JP4343385B2 - Toner and heat fixing method - Google Patents

Description

〔式中、ｘ及びｙは１以上の整数であり、ｘ＋ｙの平均値は２〜４である。ＲはＨ又はＣ₁〜Ｃ₂₀のアルキル又はアルケニル基である。〕
【００５４】
式（Ａ）で示される分子骨格を有するポリエステル樹脂は、後に詳しく説明する芳香族オキシカルボン酸及び芳香族アルコキシカルボン酸から選択される芳香族カルボン酸誘導体、又は、該カルボン酸誘導体の金属化合物と同時に溶融混練される際に、金属イオン架橋構造が形成され易く、トナーの動的弾性率曲線において明瞭な極小値（Ｇ′ｍｉｎ）を有するトナーを良好に生成し得る。
【００５５】
例えば、図２に示す後述の実施例と類似のトナーの動的弾性率曲線においては、温度１７０℃の領域の動的弾性率（Ｇ'₁₇₀）が、温度１４０℃の領域の動的弾性率（Ｇ'₁₄₀）よりも高温サイドの温度で、トナーは高粘弾性を有しているため、耐高温オフセット性に極めて優れている。
【００５６】
一方、図３に示す如き粘弾性を示す後述の比較トナーと類似処方のトナーは、温度１００乃至２００℃の領域に明確な極小値を有していなく、温度１００℃よりも高温サイドにおいても温度の上昇とともにトナーの貯蔵弾性率が低下している。この様なトナーは、耐高温オフセット性に劣り、定着可能温度領域が本発明のトナーよりも狭くなる。
【００５７】
式（Ａ）で示される分子骨格がなぜ特異的に芳香族オキシカルボン酸及び芳香族アルコキシカルボン酸から選択される芳香族カルボン酸誘導体又は、該芳香族カルボン酸誘導体の金属化合物と作用するかは十分には判明していないが、この分子鎖特有の屈曲性が相互作用しやすい配座を形成しやすいため（分子配置相互作用）と、ｐ位に電子供与性を有するフェニル基の電子供与性、また−ＣＨ＝ＣＲ−のπ電子供与性相互作用が深く係わっていると思われる。
【００５８】
本発明における主な結着樹脂であるポリエステル樹脂を生成するための二価のアルコール成分としては、例えばエチレングリコール、プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、２，３−ブタンジオール、ジエチレングリコール、トリエチレングリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、２−エチル−１，３−ヘキサンジオール、水酸化ビスフェノールＡ、また、式（Ｂ）で表わされるビスフェノール誘導体
【００５９】
【化２】

〔式中、Ｒはエチレン、プロピレン基であり、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。〕
が挙げられる。
【００６０】
また、非線形状ポリエステル樹脂を形成するための三価以上のアルコール成分としては、例えば、ソルビトール、１，２，３，６−ヘキサンテトロール、１，４−ソルビタン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、１，２，４−ブタントリオール、１，２，５−ペンタントリオール、グリセロール、２−メチルプロパントリオール、２−メチル−１，２，４−ブタントリオール、トリメチロールエタン、トリメチロールプロパン、１，３，５−トリヒドロキシベンゼンが挙げられる。三価以上の多価アルコールの使用量は、全モノマー基準で０．１〜１．９ｍｏｌ％が好ましい。
【００６１】
また、ポリエステル樹脂を生成するための二価の酸成分としては、例えば、フマル酸，マレイン酸，無水マレイン酸，コハク酸，アジピン酸，セバシン酸，マロン酸およびこれらを炭素数８〜２２の飽和もしくは不飽和の炭化水素基で置換した脂肪族系酸成分モノマー；また芳香族系酸成分モノマーとして、フタル酸，イソフタル酸，無水フタル酸，テレフタル酸およびそのエステル誘導体が挙げられる。
【００６２】
また、非線形状ポリエステル樹脂を形成するための三価以上の多価カルボン酸成分としては、例えば、１，２，４−ベンゼントリカルボン酸、１，２，５−ベンゼントリカルボン酸、１，２，４−ナフタレントリカルボン酸、２，５，７−ナフタレントリカルボン酸、１，２，４，５−ベンゼンテトラカルボン酸および、これらの無水物やエステル化合物が挙げられる。三価以上の多価カルボン酸成分の使用量は、全モノマー基準で０．１〜１．９ｍｏｌ％が好ましい。
【００６３】
本発明において、ポリエステル樹脂のＴＨＦ可溶分のＧＰＣ測定において、数平均分子量（Ｍｎ）が１３００〜９５００であり、重量平均分子量（Ｍｗ）が２６００〜１９００００であることが好ましい。
【００６４】
また、ポリエルテル樹脂の酸価は好ましくは１〜６０ｍｇＫＯＨ／ｇ、より好ましくは５〜５０ｍｇＫＯＨ／ｇであることが好ましい。
【００６５】
また、トナー化した際のＴＨＦ可溶分のＧＰＣ測定において、数平均分子量（Ｍｎ）が１５００〜１００００であり、重量平均分子量（Ｍｗ）が３０００〜１５０００００であることが好ましい。
【００６６】
ポリエステル樹脂の数平均分子量（Ｍｎ）が１３００未満の場合又は重量平均分子量（Ｍｗ）が２６００未満、もしくはトナーの数平均分子量（Ｍｎ）が１５００未満の場合又は重量平均分子量（Ｍｗ）が３０００未満の場合には、いずれも定着画像表面の平滑性は高く見た感じの鮮やかさはあるものの、耐久において高温オフセットが発生しやすくなり、さらに、長期保存安定性が低下し、現像器内でのトナー融着及びキャリア表面にトナー成分が付着してキャリアスペントの発生といった新たな問題も懸念される。さらに、カラートナー粒子の製造時のトナー原料の溶融混練時にシェアーがかかり難く、着色剤の分散性が低下し易く、よってトナーの着色力の低下やトナーの帯電量の変動が生じ易い。
【００６７】
ポリエステル樹脂の数平均分子量（Ｍｎ）が９５００を超える場合又は重量平均分子量（Ｍｗ）が１９００００を超える場合、もしくはトナーの数平均分子量（Ｍｎ）が１００００を超えるの場合又は重量平均分子量（Ｍｗ）が１５０００００を超えるの場合は、いずれも耐オフセット性に優れるものの、定着設定温度を高くせざるを得ないし、さらに、仮に顔料の分散の程度をコントロールできたとして、画像部での表面平滑性が低下してしまい色再現性が低下し易くなってしまう。
【００６８】
ポリエステル樹脂の酸価が、１ｍｇＫＯＨ／ｇ未満の場合には、耐久における帯電量の上昇、所謂チャージアップが発生しやすく、画像濃度を長期に渡って維持することが困難となる。またポリエステル樹脂の酸価が１ｍｇＫＯＨ／ｇ未満の場合には、本発明におけるワックス含有一次分散径及びドメイン径のコントロールが難しく、トナーにしたときのそれぞれの径が、４μｍ，５μｍを超えたものとなり、トナーの現像性だけでなく、保存安定性においても悪くなってしまう。これは、前述した様なポリエステル樹脂、ワックス、スチレン系共重合体のＳｐ値の関係だけでなく、極性基同士のインタラクション（ｉｎｔｅｒａｃｔｉｏｎ）が関与していると考えられる。特に低酸価（５ｍｇＫＯＨ／ｇ未満）のポリエステル樹脂においては、共重合体は、Ｎ含有モノマー，カルボキシル基含有モノマーが好ましく、より好ましくはＮ含有モノマーを含む共重合体を用いるのが良い。また高酸価（５０ｍｇＫＯＨ／ｇ以上）のポリエステル樹脂においては、該共重合体は、Ｎ含有モノマー，ヒドロキシル基含有モノマーが好ましく、より好ましくはＮ含有モノマーを含む共重合体を用いるのが良い。
【００６９】
ポリエステル樹脂の酸価が、６０ｍｇＫＯＨ／ｇを超える場合は、チャージアップ傾向はなくなるが、特に高温高湿環境時における帯電量の減少傾向、所謂チャージダウンに起因する白地カブリが発生し、画像品質の低下を招くこととなる。
【００７０】
本発明に用いられる離型剤（ワックス）としては次のものが挙げられる。低分子量ポリエチレン、低分子量ポリプロピレン、マイクロクリスタリンワックス、パラフィンワックスの如き脂肪族炭化水素系ワックス；酸化ポリエチレンワックスの如き脂肪族炭化水素系ワックスの酸化物；脂肪族炭化水素系ワックスのブロック共重合物；カルナバワックス、サゾールワックス、モンタン酸エステルワックスの如き脂肪酸エステルを主成分とするワックス；及び脱酸カルナバワックスの如き脂肪酸エステルを一部または全部を脱酸化したものなどが挙げられる。さらに、離型剤として、パルミチン酸、ステアリン酸、モンタン酸の如き飽和直鎖脂肪酸；ブランジン酸、エレオステアリン酸、バリナリン酸の如き不飽和脂肪酸；ステアリルアルコール、アラルキルアルコール、ベヘニルアルコール、カルナウビルアルコール、セリルアルコール、メリシルアルコールの如き飽和アルコール；ソルビトールの如き多価アルコール；リノール酸アミド、オレイン酸アミド、ラウリン酸アミドの如き脂肪酸アミド；メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、ヘキサメチレンビスステアリン酸アミドの如き飽和脂肪酸ビスアミド；エチレンビスオレイン酸アミド、ヘキサメチレンビスオレイン酸アミド、Ｎ，Ｎ′−ジオレイルアジピン酸アミド、Ｎ，Ｎ′−ジオレイルセバシン酸アミドの如き不飽和脂肪酸アミド；ｍ−キシレンビスステアリン酸アミド、Ｎ，Ｎ′−ジステアリルイソフタル酸アミドの如き芳香族系ビスアミド；ステアリン酸カルシウム、ラウリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウムの如き脂肪酸金属塩（一般に金属石けんといわれているもの）；脂肪族炭化水素系ワックスにスチレンやアクリル酸の如きビニルモノマーをグラフト化させたグラフトワックス；ベヘニン酸モノグリセリドの如き脂肪酸と多価アルコールの部分エステル化物；植物性油脂を水素添加することによって得られるヒドロキシル基を有するメチルエステル化合物などが挙げられる。
【００７１】
特に好ましく用いられるワックスとしては、パラフィンワックスの如き脂肪族炭化水素系ワックスである。
【００７２】
次に、本発明において用いたワックス分散剤について鋭意検討した内容に関して説明する。
【００７３】
炭化水素系ワックスのＤＳＣによって測定される昇温時の吸熱曲線において、最大吸熱ピークの極大値が５５〜８０℃にあること、また、トナーの質量を基準として０．１〜６質量%含有させることが良い。
【００７４】
ワックスの量が０．１質量％未満の場合は、特に定着オイルの塗布量を減らした場合もしくは全く使用しない場合の離型効果が得られず、６質量％よりも多い場合は、顔料の分散が悪くなり、結果的にトナーの彩度を損なうこととなる。
【００７５】
また、最大吸熱ピークが５５℃未満のワックスを用いた場合、本発明に用いられる樹脂のガラス転移温度よりも低くなるために、高温環境に放置した際にトナー表面に溶け出すため、耐ブロッキング性能が大幅に悪くなる。一方、最大吸熱ピークが８０℃より大きい場合、トナー定着溶融時にワックスが迅速に溶融トナー表面に移行できず、離型性が悪くなるために、高温オフセットが発生し易くなる。
【００７６】
炭化水素系ワックスのＧＰＣによる分子量分布において、重量平均分子量（Ｍｗ）が４００〜８００であり、数平均分子量（Ｍｎ）が４００〜６００であり、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が１．０〜２．０であることが好ましい。
【００７７】
炭化水素系ワックスの数平均分子量（Ｍｎ）が４００未満の場合又は重量平均分子量（Ｍｗ）が４００未満の場合、高温環境に放置した際にトナー表面に溶け出すため、耐ブロッキング性能が大幅に悪くなる。
【００７８】
また、炭化水素系ワックスの数平均分子量（Ｍｎ）が６００を超える場合又は重量平均分子量（Ｍｗ）が８００を超える場合、もしくは重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が２．０を超える場合、トナー定着溶融時にワックスが迅速に溶融トナー表面に移行できず、離型性が悪くなるために、高温オフセットが発生し易くなる。
【００７９】
本発明におけるメインバインダーであるポリエステル樹脂と炭化水素系ワックスとの相溶性は、元来より乏しいため、そのままの状態で添加してトナー化した際には、トナー中にワックスが偏析して存在し、遊離ワックス等も発生することから、結果的に白抜けの発生や帯電不良等の不具合が発生する。
【００８０】
本発明における共重合体樹脂のＧＰＣによる分子量分布においては、重量平均分子量（Ｍｗ）が５０００〜１０００００であり、数平均分子量（Ｍｎ）が１５００〜１５０００であり、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が２〜４０であることが良い。
【００８１】
共重合体樹脂の重量平均分子量（Ｍｗ）が５０００未満の場合、または数平均分子量（Ｍｎ）が１５００未満の場合、または重量平均分子量と数平均分子量の比（Ｍｗ／Ｍｎ）が２未満の場合、トナーの耐ブロッキング性能が著しく損なわれる。
【００８２】
共重合体樹脂の重量平均分子量（Ｍｗ）が１０００００を超える場合、または数平均分子量（Ｍｎ）が１５０００を超える場合、または重量平均分子量と数平均分子量の比（Ｍｗ／Ｍｎ）が４０を超える場合、ワックス分散剤中に微分散された炭化水素系ワックスが定着溶融時にワックスが迅速に溶融トナー表面に移行できず、離型性が悪くなるために、高温オフセットが発生し易くなる。
【００８３】
また、本発明に依る共重合体樹脂は、該トナー中にトナーの質量を基準として０．１〜２０質量％含有されていることが好ましい。
【００８４】
本発明による共重合体樹脂におけるトナーの質量を基準とした含有率が２０質量％を超える場合、メインバインダーであるポリエステル樹脂の低温定着（シャープメルト性）が損なわれるため、非オフセット温度領域が狭くなるという弊害が生じる。
【００８５】
本発明による共重合体樹脂とのグラフト重合に用いられる該ポリオレフィンは、ＤＳＣによって測定される昇温時の吸熱曲線において、最大吸熱ピークの極大値が９０〜１３０℃にあることが良い。
【００８６】
該ポリオレフィンの最大吸熱ピークの極大値が９０℃未満、もしくは１３０℃を超える場合、いずれもスチレン−アクリロニトル−（メタ）アクリル酸系共重合体とのグラフト共重合体における枝別れ構造が損なわれるために炭化水素系ワックスの微分散が行われないため、トナー化した際における炭化水素系ワックスの偏析が生じ、白抜け等の画像不良が発生する。
【００８７】
本発明においてワックス分散剤中に含有される該ポリオレフィンのＧＰＣによる分子量分散における重量平均分子量（Ｍｗ）は５００〜３００００であり、数平均分子量（Ｍｎ）は５００〜３０００であり、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は１．５〜２０であり、密度は０．９〜０．９５の低密度であることが好ましい。
【００８８】
該ポリオレフィンの重量平均分子（Ｍｎ）が５００未満の場合、または数平均分子量（Ｍｎ）が５００未満の倍、または重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は１．５未満の場合、もしくは、重量平均分子量（Ｍｗ）が３００００を超える場合、または数平均分子量（Ｍｎ）が３０００を超える場合、または重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が２０を超える場合、ワックス分散中に微分散された炭化水素系ワックスが定着時にトナー表面に有効的に染み出してこないため、耐高温オフセット性は悪化する。
【００８９】
また、該ポリオレフィンの密度が０．９５を超える（低密度ではない）場合、該共重合体樹脂とのグラフト共重合体における有効が枝分かれ構造が損なわれるため、トナー化した際における該炭化水素系の偏析が生じ、白抜け等の画像不良が発生する。
【００９０】
また、該ポリオレフィンは、該トナー中にトナーの質量を基準として０．０１〜２．０質量％、好ましくは０．１〜２．０質量％含有されていることが好ましい。
【００９１】
該ポリオレフィンにおけるトナーの質量を基準とした含有率が０．０１質量％未満の場合では添加効果が小さく、２．０質量％を超える場合、これも上述の結果と同じく、共重合体樹脂とのグラフト共重合体における有効な枝分かれ構造が損なわれるために炭化水素系ワックスの微分散が行われず、トナー化した際における該炭化水素系ワックスの偏析が生じ、白抜け等の画像不良が発生する。
【００９２】
本発明に使用する有機金属化合物としては、芳香族オキシカルボン酸及び芳香族アルコキシカルボン酸から選択される芳香族カルボン酸誘導体、該芳香族カルボン酸誘導体の金属化合物であり、さらにはサリチル酸金属化合物であることが好ましく、その金属としては、２価以上の金属原子が好ましい。２価の金属としてＭｇ²⁺，Ｃａ²⁺，Ｓｒ²⁺，Ｐｂ²⁺，Ｆｅ²⁺，Ｃｏ²⁺，Ｎｉ²⁺，Ｚｎ²⁺，Ｃｕ²⁺が挙げられる。２価の金属としては、Ｚｎ²⁺，Ｃａ²⁺，Ｍｇ²⁺，Ｓｒ²⁺が好ましい。３価以上の金属としてはＡｌ³⁺，Ｃｒ³⁺，Ｆｅ³⁺，Ｎｉ³⁺があげられる。これらの金属の中で好ましいのはＡｌ³⁺，Ｃｒ³⁺であり、特に好ましいのはＡｌ³⁺である。
【００９３】
本発明においては、有機金属化合物として、ジ−ｔｅｒｔ−ブチルサリチル酸のアルミニウム化合物が特に好ましい。
【００９４】
サリチル酸金属化合物は、例えば、サリチル酸を水酸化ナトリウム水溶液に溶解させ、２価以上の金属原子を溶融している水溶液を水酸化ナトリウム水溶液に滴下し、加熱撹拌し、次に水溶液のｐＨを調整し、室温まで冷却した後、ろ過・水洗することにより芳香族サリチル酸の金属化合物を合成し得る。ただし、上記の合成方法だけに限定されるものではない。
【００９５】
有機金属化合物は、トナーの質量基準で０．１〜１０質量％使用すると、トナーの帯電量の初期変動が少なく、現像時に必要な絶対帯電量が得られやすく、結果的にカブリや画像濃度ダウンの如き画像品質の低下がなく好ましい。
【００９６】
有機金属化合物の含有率が、トナーの質量基準として０．１質量％未満（全く加えない）であると、耐久時における帯電量が不安定となり、結果的に画像濃度の維持性に劣ることとなる。有機金属化合物の含有率が、トナーの質量基準として１０質量％を超えると、逆に耐久時にチャージアップが発生するために、画像濃度の低下を招くこととなる。
【００９７】
本発明のトナーを磁性トナーとして用いる場合、磁性トナー粒子は、磁性体を含む。その場合、磁性体は着色剤としての機能も有する。磁性材料としては、マグネタイト、マグヘマイト、フェライト等の酸化鉄、及び他の金属酸化物を含む酸化鉄；Ｆｅ，Ｃｏ，Ｎｉのような金属、あるいは、これらの金属とＡｌ，Ｃｏ，Ｃｕ，Ｐｂ，Ｍｇ，Ｎｉ，Ｓｎ，Ｚｎ，Ｓｂ，Ｂｅ，Ｂｉ，Ｃｄ，Ｃａ，Ｍｎ，Ｓｅ，Ｔｉ，Ｗ，Ｖのような金属との合金、およびこれらの混合物等が挙げられる。
【００９８】
例えば、磁性材料としては、四三酸化鉄（Ｆｅ₃Ｏ₄）、三二酸化鉄（γ−Ｆｅ₂Ｏ₃）、酸化鉄亜鉛（ＺｎＦｅ₂Ｏ₄）、酸化鉄イットリウム（Ｙ₃Ｆｅ₅Ｏ₁₂），酸化鉄カドミウム（ＣｄＦｅ₂Ｏ₄）、酸化鉄ガドリニウム（Ｇｄ₃Ｆｅ₅Ｏ₁₂）、酸化鉄銅（ＣｕＦｅ₂Ｏ₄）、酸化鉄鉛（ＰｂＦｅ₁₂Ｏ₁₉）、酸化鉄ニッケル（ＮｉＦｅ₂Ｏ₄）、酸化鉄ネオジム（ＮｄＦｅ₂Ｏ₃）、酸化鉄バリウム（ＢａＦｅ₁₂Ｏ₁₉）、酸化鉄マグネシウム（ＭｇＦｅ₂Ｏ₄）、酸化鉄マンガン（ＭｎＦｅ₂Ｏ₄）、酸化鉄ランタン（ＬａＦｅＯ₃）、鉄粉（Ｆｅ）、コバルト粉（Ｃｏ）、ニッケル粉（Ｎｉ）等が挙げられる。好適な磁性材料は四三酸化鉄，磁性フェライト又はγ−三二酸化鉄の微粉末である。
【００９９】
磁性体は平均粒径が０．１〜２μｍ（好ましくは０．１〜０．５μｍ）で、７９６ｋＡ／ｍ（１０ｋエルステッド）印加で磁気特性が抗磁力１．６〜１２ｋＡ／ｍ（２０〜１５０エルステッド）、飽和磁化５０〜２００Ａｍ²／ｋｇ（好ましくは５０〜１００Ａｍ²／ｋｇ）、残留磁化２〜２０Ａｍ²／ｋｇのものが好ましい。
【０１００】
該磁性体は、マグネットを内包する現像剤担持体上に磁気的拘束力を伴って担持される磁性一成分系現像剤として用いられる場合、トナーの質量基準で５〜１２０質量％含有するのが好ましい。
【０１０１】
また、マグネットを有していない現像剤担持体上に磁気的拘束力を伴わずに担持される系非磁性一成分現像剤として用いられる場合、磁性体をトナーの質量基準で０．１〜５質量％含有していることが好ましい。
【０１０２】
この範囲内で含有させることにり、耐久時におけるトナー飛散現象（機内汚れ）を抑えることができる。
【０１０３】
磁性体の含有率が、トナーの質量基準で５質量％を超えると、規制ブレードもしくはトナーを担持するローラー表面を著しく破損（削る）こととなり、帯電不良の原因となる。
【０１０４】
また、磁性キャリア粒子と混合されて二成分系現像剤として用いられる場合、磁性体をトナーの質量基準で０．１〜５質量％含有していることが好ましい。
【０１０５】
この範囲内で含有させることにり、現像剤を担持するローラーとの磁気的拘束力が増すために、耐久時におけるトナー飛散現象（機内汚れ）を抑えることができる。
【０１０６】
磁性体の含有率が、トナーの質量基準で５質量％を超えると、現像剤を担持するローラーとの磁気的拘束力が増し過ぎるために、画像濃度の低下を招くこととなる。
【０１０７】
本発明に用いられる着色剤としては、顔料及び／又は染料を用いることができる。
【０１０８】
例えば染料としては、Ｃ．Ｉ．ダイレクトレッド１、Ｃ．Ｉ．ダイレクトレッド４、Ｃ．Ｉ．アシッドレッド１、Ｃ．Ｉ．ベーシックレッド１、Ｃ．Ｉ．モーダントレッド３０、Ｃ．Ｉ．ダイレクトブルー１、Ｃ．Ｉ．ダイレクトブルー２、Ｃ．Ｉ．アシッドブルー９、Ｃ．Ｉ．アシッドブルー１５、Ｃ．Ｉ．ベーシックブルー３、Ｃ．Ｉ．ベーシックブルー５、Ｃ．Ｉ．モーダントブルー７、Ｃ．Ｉ．ダイレクトグリーン６、Ｃ．Ｉ．ベーシックグリーン４、Ｃ．Ｉ．ベーシックグリーン６等が挙げられる。
【０１０９】
顔料としては、ミネラルファストイエロー、ネーブルイエロー、ナフトールイエローＳ、ハンザイエローＧ、パーマネントイエローＮＣＧ、タートラジンレーキ、モリブデンオレンジ、パーマネントオレンジＧＴＲ、ピラゾロンオレンジ、ベンジジンオレンジＧ、パーマネントレッド４Ｒ、ウオッチングレッドカルシウム塩、エオシンレーキ、ブリリアントカーミン３Ｂ、マンガン紫、ファストバイオレットＢ、メチルバイオレットレーキ、コバルトブルー、アルカリブルーレーキ、ビクトリアブルーレーキ、フタロシアニンブルー、ファーストスカイブルー、インダンスレンブルーＢＣ、クロムグリーン、ピグメントグリーンＢ、マラカイトグリーンレーキ、ファイナルイエローグリーンＧ等が挙げられる。
【０１１０】
また、フルカラー画像形成用トナーとして使用する場合には、マゼンタ用着色顔料としては、Ｃ．Ｉ．ピグメントレッド１，２，３，４，５，６，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７，１８，１９，２１，２２，２３，３０，３１，３２，３７，３８，３９，４０，４１，４８，４９，５０，５１，５２，５３，５４，５５，５７，５８，６０，６３，６４，６８，８１，８３，８７，８８，８９，９０，１１２，１１４，１２２，１２３，１４４，１６３，１８４，２０２，２０６，２０７，２０９，２２１，２３８，２５４，２６９、Ｃ．Ｉ．ピグメントバイオレット１９、Ｃ．Ｉ．バットレッド１，２，１０，１３，１５，２３，２９，３５等が挙げられる。
【０１１１】
係る顔料を単独で使用しても構わないが、染料と顔料と併用してその鮮明度を向上させた方がフルカラー画像の画質の点から、より好ましい。マゼンタ用染料としては、Ｃ．Ｉ．ソルベントレッド１，３，８，２３，２４，２５，２７，３０，４９，８１，８２，８３，８４，１００，１０９，１２１、Ｃ．Ｉ．ディスパースレッド９、Ｃ．Ｉ．ソルベントバイオレット８，１３，１４，２１，２７、Ｃ．Ｉ．ディスパースバイオレット１の如き油溶染料；Ｃ．Ｉ．ベーシックレッド１，２，９，１２，１３，１４，１５，１７，１８，２２，２３，２４，２７，２９，３２，３４，３５，３６，３７，３８，３９，４０、Ｃ．Ｉ．ベーシックバイオレット１，３，７，１０，１４，１５，２１，２５，２６，２７，２８の如き塩基性染料が挙げられる。
【０１１２】
シアン用着色顔料としては、Ｃ．Ｉ．ピグメントブルー２，３，１５，１６，１７、Ｃ．Ｉ．アシッドブルー６、Ｃ．Ｉ．アシッドブルー４５又はフタロシアニン骨格にフタルイミドメチル基を１〜５個置換した銅フタロシアニン顔料等である。
【０１１３】
イエロー用着色顔料としては、Ｃ．Ｉ．ピグメントイエロー１，２，３，４，５，６，７，１０，１１，１２，１３，１４，１５，１６，１７，２３，６５，７３，８３，９３，９７，１８０、Ｃ．Ｉ．バットイエロー１，３，２０等が挙げられる。
【０１１４】
着色剤の使用量は、結着樹脂１００質量部に対して、１乃至１５質量部、好ましくは３乃至１２質量部、より好ましくは４乃至１０質量部含有していることが良い。
【０１１５】
着色剤の含有量が１５質量部より多い場合には、透明性が低下し、加えて人間の肌色に代表される様な中間色の再現性も低下し易くなり、更にはトナーの帯電性の安定性が低下し、目的とする帯電量が得られにくくなる。
【０１１６】
着色剤の含有量が１質量部より少ない場合には、目的とする着色力が得られ難く、高い画像濃度の高品位画像が得られ難い。
【０１１７】
トナー粒子には、流動性向上剤が外添されていることが画質向上のために好ましい。
【０１１８】
流動性向上剤としては、トナー粒子に外添することにより、流動性が添加前後を比較すると増加し得るものである。例えば、フッ化ビニリデン微粉末、ポリテトラフルオロエチレン微粉末の如きフッ素系樹脂粉末；湿式製法によるシリカ微粉末、乾式製法によるシリカ微粉末の如きシリカ微粉末、それらシリカ微粉末をシランカップリング剤、チタンカップリング剤、シリコーンオイルの如き処理剤により表面処理を施した処理シリカ微粉末；酸化チタン微粉末；アルミナ微粉末、処理酸化チタン微粉末、処理酸化アルミナ微粉末が挙げられる。
【０１１９】
流動性向上剤は、ＢＥＴ法で測定した窒素吸着により比表面積が３０ｍ²／ｇ以上、好ましくは５０ｍ²／ｇ以上のものが良好な結果を与える。トナー粒子１００質量部に対して流動性向上剤０．０１〜８質量部、好ましくは０．１〜４質量部使用するのが良い。
【０１２０】
トナー粒子は結着樹脂、着色剤、有機金属化合物及びその他の任意成分の添加剤をヘンシェルミキサー、ボールミルの如き混合機により充分混合し、ニーダー、エクストルーダーの如き熱混練機を用いて溶融、捏和及び練肉し、溶融混練物を冷却固化後に固化物を粉砕し、粉砕物を分級することにより所定の平均粒径のトナー粒子を生成することができる。
【０１２１】
さらに、流動性向上剤とトナー粒子をヘンシェルミキサーの如き混合機により充分混合し、トナー粒子表面に流動性向上剤を有するトナーを得ることができる。
【０１２２】
本発明において、トナーの重量平均粒径（Ｄ₄）は、３．０乃至１５．０μｍ、好ましくは４．０乃至１２．０μｍが良い。
【０１２３】
トナーの重量平均粒径（Ｄ₄）が３．０μｍ未満の場合には、帯電安定化が達成しづらくなり、耐久において、カブリやトナー飛散が発生しやすくなる。
【０１２４】
トナーの重量平均粒径（Ｄ₄）が１５．０μｍを超える場合には、ハーフトーン部の再現性が大きく低下し、得られた画像はガサついた画像になってしまう。
【０１２５】
次に、本発明のトナーを適用し、電子写真法によりフルカラー画像を形成する方法を図４を参照しながら説明する。
【０１２６】
図４は、電子写真法によりフルカラーの画像を形成するための画像形成装置の一例を示す概略構成図である。図４の画像形成装置は、フルカラー複写機又はフルカラープリンタとして使用される。フルカラー複写機の場合は、図３に示すように、上部にデジタルカラー画像リーダ部、下部にデジタルカラー画像プリンタ部を有する。
【０１２７】
画像リーダ部において、原稿３０を原稿台ガラス３１上に載せ、露光ランプ３２により露光走査することにより、原稿３０からの反射光像をレンズ３３によりフルカラーセンサ３４に集光し、カラー色分解画像信号を得る。カラー色分解画像信号は、増幅回路（図示せず）を経てビデオ処理ユニット（図示せず）にて処理を施され、デジタル画像プリンタ部に送出される。
【０１２８】
画像プリンタ部において、像担持体である感光ドラム１は、たとえば有機光導電体を有する感光層を有し、矢印方向に回転自在に担持されている。感光ドラム１の回りには、前露光ランプ１１、コロナ帯電器２、レーザ露光光学系３、電位センサ１２、色の異なる４個の現像器４Ｙ、４Ｃ、４Ｍ、４Ｂ、ドラム上光量検知手段１３、転写装置５およびクリーニング器６が配置されている。
【０１２９】
レーザ露光光学系において、リーダ部からの画像信号は、レーザ出力部（図示せず）にてイメージスキャン露光の光信号に変換され、変換されたレーザ光がポリゴンミラー３ａで反射され、レンズ３ｂおよびミラー３ｃを介して、感光ドラム１の面上に投影される。
【０１３０】
プリンタ部は、画像形成時、感光ドラム１を矢印方向に回転させ、前露光ランプ１１で除電した後に感光ドラム１を帯電器２により一様にマイナス帯電させて、各分解色ごとに光像Ｅを照射し、感光ドラム１上に静電荷像を形成する。
【０１３１】
次に、所定の現像器を動作させて感光ドラム１上の静電荷像を現像し、感光ドラム１上にトナーによるトナー画像を形成する。現像器４Ｙ、４Ｃ、４Ｍ、４Ｂは、それぞれの偏心カム２４Ｙ、２４Ｃ、２４Ｍ、２４Ｂの動作により、各分解色に応じて択一的に感光ドラム１に接近して、現像を行う。
【０１３２】
転写装置は、転写ドラム５ａ、転写帯電器５ｂ、記録材としての転写材を静電吸着するための吸着帯電器５ｃおよびこれと対向する吸着ローラ５ｇ、そして内側帯電器５ｄ、外側帯電器５ｅ、分離帯電器５ｈを有している。転写ドラム５ａは、回転駆動可能に軸支され、その周面の開口域に転写材を担持する転写材担持体である転写シート５ｆが、円筒上に一体的に調節されている。転写シート５ｆにはポリカーボネートフィルムの如き樹脂フィルムが使用される。
【０１３３】
転写材はカセット７ａ、７ｂまたは７ｃから転写シート搬送系を通って転写ドラム５ａに搬送され、転写ドラム５ａ上に担持される。転写ドラム５ａ上に担持された転写材は、転写ドラム５ａの回転にともない感光ドラム１と対向した転写位置に繰り返し搬送され、転写位置を通過する過程で転写帯電器５ｂの作用により、転写材上に感光ドラム１上のトナー画像が転写される。
【０１３４】
トナー画像は、感光体から直接転写材へ転写されても良く、また、感光体上のトナー画像を中間転写体へ転写し、中間転写体からトナー画像を転写材へ転写しても良い。
【０１３５】
上記の画像形成工程を、イエロー（Ｙ）、マゼンタ（Ｍ）、シアン（Ｃ）およびブラック（Ｂ）について繰り返し、転写ドラム５上の転写材上に４色のトナー画像を重ねたカラー画像が得られる。
【０１３６】
このようにして４色のトナー画像が転写された転写材は、分離爪８ａ、分離押上げコロ８ｂおよび分離帯電器５ｈの作用により、転写ドラム５ａから分離して加熱加圧定着器９に送られ、そこで加熱加圧定着することによりトナーの混色、発色および転写材への固定が行われて、フルカラーの定着画像とされたのちトレイ１０に排紙され、フルカラー画像の形成が終了する。
【０１３７】
このとき、加熱加圧定着器９での定着動作速度は、本体のプロセススピード（例えば１６０ｍｍ／ｓｅｃ）より遅い（例えば９０ｍｍ／ｓｅｃ）で行われる。これは、トナーが二層から四層積層された未定着画像を溶融混色させる場合、十分な加熱量をトナーに与えなければならないためで、現像速度より遅い速度で定着を行うことによりトナーに対する加熱量を多くしている。
【０１３８】
図５において、定着手段である定着ローラー３９は、例えば厚さ５ｍｍのアルミ製の芯金４１上に厚さ２ｍｍのＲＴＶ（室温加硫型、ＪＩＳ−Ａ硬度２０）シリコーンゴム層４２、この外側に厚さ５０μｍのポリテトラフルオロエチレン（ＰＴＦＥ）層４３を有している。
【０１３９】
一方、加圧手段である加圧ローラー４０は、例えば厚さ５ｍｍのアルミの芯金４４の上に厚さ２ｍｍのＲＴＶシリコーンゴム層４５（ゴム硬度ＪＩＳ−Ａ硬度４０）、この外側に厚さ１５０μｍ層のＰＴＦＥ層を有している。
【０１４０】
図５において、定着ローラー、加圧ローラー共にその外径は、６０ｍｍφであるが、加圧ローラーの方が硬度が高いため、白紙による排紙テストでは、両ローラーの中心線を結ぶ線に対しての垂線より、排紙方向は、加圧ローラー側になる。この排紙方向を加圧ローラー側にすることが、画像面積の大きいコピー画像を定着する場合の定着支持体の定着ローラー巻きつき防止に極めて重要である。排紙方向を加圧ローラー側にする手段としては、前記した硬度差をつける方法、或いは、加圧ローラーの径を定着ローラーよりも小さくする方法、加圧ローラー側の設定温度を定着ローラーよりも高くし、定着紙背面、つまり加圧ローラー側の紙面の水分をより多く蒸発させることにより、ごく少量の紙のちぢみを利用する方法などが挙げられる。
【０１４１】
また、上記定着ローラー３９には発熱手段であるハロゲンヒータ４６が配設され、加圧ローラー４０には同じくハロゲンヒータ４７が芯金内に配設されて両面からの加熱を行っている。定着ローラー３９及び加圧ローラー４０に当接されたサーミスタ４８ａ及び４８ｂにより定着ローラ３９及び加圧ローラーの温度が検知され、この検知温度に基づき制御装置４９ａ及び４９ｂによりハロゲンヒータ４６及び４７がそれぞれ制御され、定着ローラー３９の温度及び加圧ローラー４０の温度が共に一定の温度（例えば、１６０℃±１０℃に保つように制御される。定着ローラー３９と加圧ローラー４０は加圧機構（図示せず）によって総圧約３９０Ｎ（４０ｋｇｆ）で加圧されている。
【０１４２】
図５においてＣはオイル含浸紙ウェブによる定着ローラークリーニング装置であり、Ｃ１は加圧ローラーに付着したオイル及び汚れを除去するためのクリーニングブレードである。紙ウェブ含浸用オイルは、５０〜３０００ｃｓのシリコーンオイル（ジメチルシリコーンオイル、ジフェニルシリコーンオイル等のシリコーンオイル類）を用いることが、オイル塗布量を少量で一定に供給することが容易であり、かつ、定着画像の品位（特に均一光沢性、オイル痕）の高いものとなる。また、オイルを塗布しない場合は、Ｃのクリーニング装置を取り外すか、オイルを含浸していない紙、または布ウェブを用いるか、クリーニングブレード、もしくはクリーニングパッド、クリーニングローラーを用いるのが良い。
【０１４３】
クリーニング装置Ｃはノーメックス（商品名）より成る不織布ウェブ５６を押圧ローラー５５にて定着ローラー３９に押し当ててクリーニングしている。該ウェブ５６は巻き取り装置（図示せず）により適宜巻き取られ、定着ローラ３９との当接部にトナー等が堆積しないようにされている。
【０１４４】
本発明のトナーは、低温定着性及び耐高温オフセット性に優れているので離型剤の塗布量を少なくすることが可能であり、また、クリーニング装置の汚れ量も少ない。
【０１４５】
本発明のトナーのトナー像は、定着ローラの表面温度１５０℃±３０℃の温度条件で加熱加圧定着するのが良く、該記録材への該トナー画像の定着時に、該定着部材から該記録材のトナー画像の定着面に供給されるシリコーンオイルの記録材単位面積当たりの塗布量が０〜１×１０^-7ｇ／ｃｍ²であるのが良い。
【０１４６】
塗布量が１×１０^-7ｇ／ｃｍ²を超える場合は、該記録材のギラツキが大きく、特に文字画像の視認性を著しく阻害する。
【０１４７】
上記の画像形成プロセスによって、本発明のトナーを有するカラートナー画像が記録材シートに定着されることによって記録シートに形成されたカラー画像が得られる。
【０１４８】
結着樹脂及びトナー粒子における各物性の測定方法を以下に説明する。
【０１４９】
（１）集束イオンビーム加工観察装置によるトナー及び樹脂の断面観察方法
集束イオンビーム加工観察装置（ＦＩＢ装置）、ＦＢ−２０００Ａ（日立製作所製）を用い、加工観察する。次に測定資料の作製方法の一例を示す。
【０１５０】
ＦＩＢ用試料台上にカーボンペーストを塗る又は導電テープを貼って、その上から測定試料を少量固着させ、それを蒸着することにより作製した。
【０１５１】
その作製した試料をＦＩＢ装置にて加工表面を保護した後に、粗加工として試料断面を削り出し、その後中加工、仕上げ加工とビームのエネルギーを小さくして加工する。最終的な観察時にはエネルギーがもっとも小さいビームを利用して観察を行う。
【０１５２】
本発明におけるワックスを含む一次平均分散粒子径及びドメイン径（局在化平均分散径）は、以下の様にして求める。
【０１５３】
本発明ドメイン−マトリックス樹脂組成物を、１０μｍ程度の大きさに粉砕したものをサンプルに用いる。観察手順は上述のごとく行う。１回目の観察終了後、例えば、着目したある１つのドメインと、ワックスを含む一次分散粒径を測定する。次にビームのエネルギーを調節しながら、少しずつ削り出しを行い、着目したドメインと、一次分散粒径の変化を測定し、観測画面縦横（ｘ−ｙ）方向と、深さ（奥行き）（ｚ）方向の径を得る。ドメイン及び一次分散径の最大径は、これらの測定結果を図６のごとくプロットし、内挿或いは外挿により求める。測定数は、サンプル１つあたり、ドメイン及び一次分散粒子各１０個測定、サンプル５個、計５０サンプルずつ測定する。これらの最大径の平均を出し、それぞれ、一次平均分散径、平均ドメイン径とした。
【０１５４】
トナーについても同様の方法で行う。但しトナーにおいては、一次分散粒子が一部合一化している場合が観察されるが、それは、１つの一次分散粒子と見なして、平均径を出した。
【０１５５】
（２）酸価（ＪＩＳ酸価）の測定
サンプル２〜１０ｇを２００〜３００ｍｌの三角フラスコに秤量し、メタノール：トルエン＝３０：７０の混合溶媒約５０ｍｌを加えて樹脂を溶解する。溶解性が悪いようであれば少量のアセトンを加えてもよい。０．１％のブロムチモールブルーとフェノールレッドの混合指示薬を用い、予め標定されたＮ／１０カ性カリ〜アルコール溶液で滴定し、アルコールカリ液の消費量からつぎの計算で酸価を求める。
【０１５６】
酸価＝ＫＯＨ（ｍｌ数）×ｆ×５６．１／試料重量
（ただしｆはＮ／１０ＫＯＨのファクター）
【０１５７】
（３）分子量分布測定用のサンプル作製
トナーの分子量を測定する場合は、ＴＨＦに溶解させ、ソックスレー還流により６時間抽出し、溶解したものをサンプルとして測定する。
【０１５８】
ポリエステル、共重合体樹脂、ワックスの測定用サンプルは、先ず、トナーを酢酸エチル可溶分・不溶分に分離し、可溶分をポリエステル樹脂分子量測定サンプルとする。不溶分は、さらに溶媒除去後、ＴＨＦ可溶分と不溶分に分離し、可溶分を共重合体樹脂、不溶分をワックスとして、分子量を測定する。
【０１５９】
（４）ＧＰＣによる分子量の測定（ポリエステル樹脂、共重合体類）
ゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるクロマトグラムの分子量は次の条件で測定される。
【０１６０】
４０℃のヒートチャンバー中でカラムを安定化させ、この温度におけるカラムに、溶媒としてテトラヒドロフラン（ＴＨＦ）を毎分１ｍｌの流速で流し、試料濃度として０．０５〜０．６質量％に調整した樹脂のＴＨＦ試料溶液を５０〜２００μｌ注入して測定する。試料の分子量測定にあたっては、試料の有する分子量分布を、数種の単分散ポリスチレン標準試料により作成された検量線の対数値とカウント数との関係から算出する。検量線作成用の標準ポリスチレン試料としては、例えば、Ｐｒｅｓｓｕｒｅ Ｃｈｅｍｉｃａｌ Ｃｏ．製あるいは、東洋ソーダ工業社製の分子量が６×１０²，２．１×１０³，４×１０³，１．７５×１０⁴，５．１×１０⁴，１．１×１０⁵，３．９×１０⁵，８．６×１０⁵，２×１０⁶，４．４８×１０⁶のものを用い、少なくとも１０点程度の標準ポリスチレン試料を用いるのが適当である。検出器にはＲＩ（屈折率）検出器を用いる。
【０１６１】
カラムとしては、１０³〜２×１０⁶の分子量領域を的確に測定するために、市販のポリスチレンゲルカラムを複数組合せるのが良く、例えば、Ｗａｔｅｒｓ社製のμ−ｓｔｙｒａｇｅｌ ５００，１０³，１０⁴，１０⁵の組合せや、昭和電工社製のｓｈｏｄｅｘ ＫＡ−８０１，８０２，８０３，８０４，８０５，８０６，８０７の組合せが好ましい。
【０１６２】
（５）ＧＰＣによる分子量の測定（ポリオレフィン、炭化水素系ワックス類）
（ＧＰＣ測定条件）
・装置：ＧＰＣ−１５０（ウォーターズ社）
・カラム：ＧＭＨ−ＨＴ３０ｃｍ２連（東ソー社製）
・温度：１３５℃
・溶媒：ｏ−ジクロロベンゼン（０．１％アイオソール添加）
・流速：１．０ｍｌ／ｍｉｎ
・試料：０．１５％の試料を０．４ｍｌ注入
以上の条件で測定し、試料の分子量算出にあたっては単分散ポリスチレン標準試料により作成した分子量較正曲線を使用する。さらに、Ｍａｒｋ−Ｈｏｕｗｉｎｋ粘度式から導き出される換算式でポリスチレン換算することによって算出される。
【０１６３】
（６）ワックス及びトナーの極大吸熱ピークの測定
示差走査熱量測定装置（ＤＳＣ測定装置）、ＤＳＣ−７（パーキンエルマー社製）を用い測定する。測定試料は５〜２０ｍｇ、好ましくは１０ｍｇを精密に秤量する。これをアルミパン中に入れ、リファレンスとして空のアルミパンを用い、測定温度範囲３０〜２００℃の間で、昇温速度１０℃／ｍｉｎで常温常湿下で測定を行う。この昇温過程で、温度３０〜１６０℃の範囲におけるメインピークの吸熱ピークが得られる。吸熱ピークとは、言うまでもなく、その中で極大の値を示す温度のことである。ポリオレフィンの吸熱ピークは、含有量が少なく、検出しづらいことが多い。この様なときは、酢酸エチルでポリエステル樹脂を溶解分離し、いわゆる濃縮したサンプルを用いて測定するのが良い（炭化水素ワックスも同様な方法で吸熱ピークを測定してもかまわない。…検出しづらい場合）。
【０１６４】
（７）トナー粒子又はトナーの粒度分布の測定
測定装置としては、コールターカウンターＴＡ−ＩＩ或いはコールターマルチサイザーＩＩ（コールター社製）を用いる。電解液は、１級塩化ナトリウムを用いて、約１％ＮｃＣｌ水溶液を調製する。例えば、ＩＳＯＴＯＮ（登録商標）−ＩＩ（コールターサイエンティフィックジャパン社製）が使用できる。測定方法としては、前記電解水溶液１００〜１５０ｍｌ中に分散剤として、界面活性剤（好ましくはアルキルベンゼンスルホン塩酸）を、０．１〜５ｍｌを加え、さらに測定試料を２〜２０ｍｇ加える。試料を懸濁した電解液は、超音波分散器で約１〜３分間分散処理を行い、前記測定装置により、アパーチャーとして１００μｍアパーチャーを用いて、トナー粒子の体積及び個数を各チャンネルごとに測定して、トナーの体積分布と個数分布とを算出する。それから、トナー粒子の体積分布から求めた質量基準のトナー粒子又はトナーの質量平均粒径（Ｄ₄）及び体積平均粒径（Ｄ_v）（各チャンネルの中央値をチャンネル毎の代表値とする）を求める。
【０１６５】
チャンネルとしては、２．００〜２．５２μｍ；２．５２〜３．１７μｍ；３．１７〜４．００μｍ；４．００〜５．０４μｍ；５．０４〜６．３５μｍ；６．３５〜８．００μｍ；８．００〜１０．０８μｍ；１０．０８〜１２．７０μｍ；１２．７０〜１６．００μｍ；１６．００〜２０．２０μｍ；２０．２０〜２５．４０μｍ；２５．４０〜３２．００μｍ；３２〜４０．３０μｍの１３チャンネルを用いる。
【０１６６】
（８）摩擦帯電量の測定
図７は摩擦帯電量を測定する装置の説明図である。底に５００メッシュのスクリーン８３のある金属製の測定容器８２に、摩擦帯電量を測定しようとする試料とキャリアとの混合物、すなわち、トナーの場合には、トナーとキャリアの質量比１：１９の混合物、また、外添剤の場合には、１：９９の混合物を５０乃至１００ｍｌ容器のポリエチレン製の瓶に入れ、約１０乃至４０秒間手で振とうし、該混合物（現像剤）約０．５乃至１．５ｇを入れ金属製のフタ８４をする。この時の測定容器８２全体の質量を秤りＷ₁（ｇ）とする。次に吸引機８１（測定容器８２と接する部分は少なくとも絶縁体）において、吸引口５７から吸引し風量調節弁８６を調整して真空計８５の圧力を２５０ｍｍＡｑとする。この状態で充分、好ましくは２分間吸引を行いトナーを吸引除去する。この時の電位計８９の電位をＶ（ボルト）とする。ここで８８はコンデンサーであり容量をＣ（ｍＦ）とする。また、吸引後の測定容器全体の質量を秤りＷ₂（ｇ）とする。この試料の摩擦帯電量（ｍＣ／ｋｇ）は下式の如く算出される。
【０１６７】
試料の摩擦帯電量（ｍＣ／ｋｇ）＝Ｃ×Ｖ／（Ｗ₁−Ｗ₂）
（但し、測定条件は２３℃，６０％ＲＨとする。）
【０１６８】
【実施例】
以下、本発明のトナー及び加熱定着方法の実施例について述べるが、本発明はこれらの例に限定されるものではない。
【０１６９】
［樹脂製造例］
・低密度ポリエチレン ２０質量部
（Ｍｗ１４００，Ｍｎ８５０，吸熱ピーク１００℃）
・スチレン ６４質量部
・ｎ−ブチルアクリレート １３．５質量部
・アクリロニトリル ２．５質量部
をオートクレーブに仕込み、系内をＮ₂置換後、昇温攪拌しながら１８０℃に保持した。系内に、２質量％のｔ−ブチルハイドロパーオキシドのキシレン溶液５０質量部を５時間連続的に滴下し、冷却後溶媒を分離除去し、ポリエチレンに共重合体が一部グラフトしたものと共重合体樹脂及び未反応ポリエチレンとの混合樹脂を得た。混合樹脂中の共重合体の分子量を測定したところ、Ｍｗ７０００，Ｍｎ３０００であった。
【０１７０】
次に、
・テレフタル酸 ２８ｍｏｌ％
・ｎ−ドデセニルコハク酸 １７ｍｏｌ％
・無水トリメリット酸 ５ｍｏｌ％
・（Ｂ）式で示されるビスフェノール ５０ｍｏｌ％
（Ｒ：プロピレン，ｘ＋ｙ≒２．２）
を縮合重合し、Ｍｗ１７０００，Ｍｎ７０００，ガラス転移温度（Ｔｇ）６５℃，酸価１２ｍｇＫＯＨ／ｇのポリエステル樹脂を得た。反応系内を１５０℃でポリエステル樹脂を溶融させながら、上記混合樹脂をポリエステル樹脂１００質量部に対し５質量部添加・混合した。さらに、炭化水素系ワックス（Ｍｗ６００，Ｍｎ５１０，吸熱ピーク６４℃）をポリエステル樹脂１００質量部に対し４質量部添加・混合した。
【０１７１】
以上のようにして得られた樹脂を樹脂Ｉとする。
【０１７２】
この樹脂ＩをＦＩＢ加工観察したところ、ポリエステル樹脂のマトリックス中に、ワックスを含む一次平均分散径が０．０４μｍであり、ドメイン径が２．５μｍであった。
【０１７３】
以下、同様にして、モノマー組成、開始剤の種類・量、ポリオレフィンの種類・量、混合比、ポリエステル樹脂の組成、炭化水素ワックスの種類・量、反応温度等の諸条件を変え、表１に示すドメイン−マトリックス樹脂組成物ＩＩ〜ＩＸを得た。
【０１７４】
【表１】

【０１７５】
＜実施例１＞
表２の処方にてトナーを作製した。ここで、ブラック，シアン，イエロー，マゼンタの各顔料は、その分散性を良くし、彩度・明度を上げる目的で、メインバインダーと同じポリエステル樹脂を用いて３０質量％の高濃度で予めマスターバッチを作製し、表２に示した顔料量になるように本発明樹脂とマスターバッチを秤量し、荷電制御剤を添加し、ヘンシェルミキサーで混合した。この後、二軸式の押出混練装置で溶融混練し、冷却・粉砕・分級して表２に示したブラック，シアン，イエロー，マゼンタの各トナー分級品を得た。
【０１７６】
これらのトナー分級品に、イソブチルトリメトキシシラン１０質量％で表面処理した酸化チタンを１．０質量％外添・混合し、各色トナーとした。
【０１７７】
また、これら外添したトナーと、シリコーン樹脂で表面コートしたフェライトキャリア粒子（平均粒径５０μｍ）とを、トナー濃度が６質量％になるように混合し、二成分系フルカラー用現像剤とした。
【０１７８】
【表２】

【０１７９】
定着可能温度領域の評価は、定着ユニットを取り外した市販の普通紙フルカラー複写機（カラーレーザー複写機ＣＬＣ９００；キヤノン製）にて上記二成分シアン現像剤を用いて未定着画像を常温常湿（Ｎ／Ｎ；２３℃，６０％）環境下で出力し、図５に示す構成の定着試験器で設定温度を変更しながら定着画像を出力し、グロス（光沢度）を測定することにより評価した。グロス７％以上の領域を混色領域とした。
【０１８０】
さらに、この定着ユニット（ウェブによるオイル塗布装置を外し、クリーニングパッドを付けた）を装着し、常温低湿（Ｎ／Ｌ；２３℃，５％）及び高温高湿（Ｈ／Ｈ；３０℃，８０％）環境下での画出し耐久テストを行った。
【０１８１】
なお、グロス（光沢度）測定に関しては、ＶＧ−１０型光沢度計（日本電色製）を用い、色度測定に用いた各ベタ画像を試料として、測定を行う。
【０１８２】
測定としては、まず定電圧装置により６Ｖにセットする。次いで投光角度，受光角度をそれぞれ６０°に合わせる。０点調整及び標準板を用い、標準設定の後に試料台の上に前記試料画像を置き、さらに白色紙を３枚上に重ね測定を行い、標示部に示される数値を％単位で読みとる。この時Ｓ，Ｓ／１０切替ＳＷはＳに合わせ、角度，感度切替ＳＷは４５−６０に合わせる。
【０１８３】
これらの評価結果を表４に示した。画像濃度は、カラー反射濃度計（Ｘ−ＲＩＴＥ ４０４Ａ；Ｘ−Ｒｉｔｅ社製）で測定した。
【０１８４】
表４に示す通り、定着特性に関し十分な定着領域・混色領域のものであり、ＯＨＴ光透性も高く、ＯＨＴ混色画像の透過画像の色再現範囲も十分広いものであった。また、Ｎ／Ｌ，Ｈ／Ｈでの画像耐久評価においても、安定した現像性を示し、保存安定性も良好な結果が得られた。また、Ｎ／Ｌ，Ｈ／Ｈでのフルカラー画像においても色再現領域の広いものであった。さらに、定着器に付けたクリーニングパッドの汚れも少なく、問題のないレベルであった。
【０１８５】
＜実施例２〜７＞
表３の処方にて実施例１と同様にしてシアントナー２〜７を作製した。これらのトナー及び現像剤を実施例１と同様に評価し、その結果を表４に示した。
【０１８６】
＜比較例１＞
実施例１で用いたポリエステル樹脂 ８８質量部、炭化水素ワックス ５．７質量部、シアンマスターバッチ １３．３質量部及び荷電制御剤 ３質量部をヘンシェルミキサーで混合し、その後実施例１と同様にトナー及び現像剤を作製し、同様に評価した。
【０１８７】
ＦＩＢによる観察では、ワックスの一次分散平均径は４．５μｍであり、一次分散粒子が形成しているドメインは観測されなかった。
【０１８８】
定着評価・画出し評価結果を表４に示した。
【０１８９】
【表３】

【０１９０】
【表４】

【０１９１】
【発明の効果】
本発明によれば、ＯＨＰでの透明性が良好で、耐オフセット性と定着性に優れ、長期間の放置後でも放置前と同様な現像性を有するカラートナーを得ることができる。
【図面の簡単な説明】
【図１】加工観察による写真に基づき描いたワックス分散又はドメインの形成を示す図である。
【図２】本発明のトナーの動的弾性率曲線の一例を示す図である。
【図３】従来のトナーの動的弾性率曲線の一例を示す図である。
【図４】本発明のトナーを用いる画像形成装置の一例を示す概略的断面図である。
【図５】加熱加圧定着手段の一例を示す概略的説明図である。
【図６】ワックスを含む一次平均分散径及びドメイン径の測定におけるデータをプロットしたものの一例を示す図である。
【図７】トナーの摩擦帯電量を測定するための装置の概略図である。
【符号の説明】
１ 感光ドラム（像担持体）
４ 現像器
９ 加熱加圧定着器[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner used for developing an electrostatic image formed in an image forming method such as an electrophotographic method, an electrostatic recording method, and an electrostatic printing method, and a heat fixing method.
[0002]
[Prior art]
In recent years, the proposed full-color copying machine uses four photosensitive members and a belt-like transfer member, and uses cyan toner, magenta toner, yellow toner and black toner for the electrostatic image formed on each photosensitive member. After development, the transfer material is transported between the photoconductor and belt transfer body and transferred between straight passes, and then a full color image is formed, or the surface of the transfer body facing the photoconductor has a mechanical action such as electrostatic force or gripper. In general, a method for obtaining a full-color image by winding a transfer material and performing a development-transfer process four times is generally used.
[0003]
As toners mounted on these full-color copying machines, it is necessary that the toners are sufficiently mixed in the heat and pressure fixing step without impairing the color reproducibility and the overhead projector (OHP) image transparency.
[0004]
The full-color image toner is preferably a low molecular weight binder resin having a sharp melt property as compared with a black toner for a general black-and-white copying machine. However, when a sharp melt binder resin is used, when the toner is melted in the heat and pressure fixing step, the self-cohesion force of the binder resin is low, and thus a problem with high temperature offset resistance is likely to occur.
[0005]
In general black toner for black-and-white copying machines, a relatively high crystalline wax typified by polyethylene wax or polypropylene wax is used as a release agent in order to improve high temperature offset resistance during fixing. For example, it has been proposed in Japanese Patent Publication No. 52-3304, Japanese Patent Publication No. 52-3305, and Japanese Patent Application Laid-Open No. 57-52574. However, in the full-color image toner, the transparency is hindered when it is projected with OHP due to the high crystallinity of the release agent itself and the difference in refractive index from the material of the OHP sheet, and the projected image is saturated. And the brightness is low.
[0006]
In order to solve this problem, methods for reducing the crystallinity of wax by using a nucleating material in combination with wax have been proposed in JP-A-4-149559 and JP-A-4-107467.
[0007]
Further, methods using a wax having a low crystallinity have been proposed in JP-A-4-301835 and JP-A-5-61238. As a wax having a relatively high transparency and a low melting point, there is a montan-based wax, and the use of a montan-based wax is disclosed in JP-A-1-185660, JP-A-1-185661, JP-A-1-185661, and JP-A-1. No. 1-185663 and JP-A-1-238672 have been proposed.
[0008]
However, these waxes do not satisfy all of transparency in OHP, low-temperature fixability at the time of heat and pressure fixing, and high-temperature offset resistance. For this reason, in ordinary color toners, an oil such as silicone oil or fluorine oil is applied to the heat fixing roller without adding a release agent as much as possible to improve high-temperature offset resistance and transparency with OHP.
[0009]
However, the fixed image obtained in this way has excess oil attached to its surface. In some cases, the oil adheres to the photoconductor and becomes contaminated, or the oil swells the fixing roller and shortens the life of the fixing roller.
[0010]
In order not to generate oil streaks on the fixed image, it is necessary to supply the oil uniformly and quantitatively on the surface of the fixing roller, and the fixing device tends to increase in size.
[0011]
Therefore, it is a toner in which the occurrence of offset is suppressed in a heat and pressure fixing means that does not use oil to prevent high temperature offset or uses a small amount of oil, and further, transparency of a fixed image. Toners that excel in the quality are awaited.
[0012]
In view of this, Japanese Patent Laid-Open Nos. 8-314300 and 8-50368 propose toner and image forming methods that do not use fixing oil by encapsulating wax by a polymerization suspension method.
[0013]
However, with these toners, oil streaks on the fixed image are suppressed, but it is necessary to encapsulate a large amount of wax inside the toner, and a binder mainly composed of styrene-acryl is used. Unevenness on the surface is inevitable, and as a result, it is difficult to say that the OHP permeability is satisfactory.
[0014]
At the same time, the recorded images of these toners inevitably have a low gloss, so there is a merit that a good image without a sense of incongruity can be obtained in a graphic image in which graphs and character portions are mixed, but a pictorial image. In the toner, since the toner after fixing is not sufficiently dissolved, a toner having excellent secondary color mixing, a wide color reproduction range, and excellent OHP permeability is desired.
[0015]
[Problems to be solved by the invention]
An object of the present invention is to provide a toner and a heat fixing method that solve the above-described problems.
[0016]
An object of the present invention is to provide a toner and a heat fixing method capable of fixing without applying a large amount of oil or without applying any oil.
[0017]
An object of the present invention is to provide a toner having a wide color reproduction range and a heat fixing method because transparency in OHP is good and secondary color mixing is good.
[0018]
An object of the present invention is to provide a toner excellent in low-temperature fixability and excellent in high-temperature offset resistance and a heat fixing method.
[0019]
An object of the present invention is to provide a toner excellent in blocking resistance when left in a high temperature environment and a heat fixing method.
[0020]
[Means for Solving the Problems]
  Specifically, the present invention is a toner having at least (i) a domain-matrix resin composition in which a domain containing a wax is formed in a matrix of a polyester resin, and (ii) a colorant,
  Focused ion beam (F) of the tonerIB) In the observation by the processing observation apparatus, the primary dispersed particles having a wax-containing primary average dispersed particle size of 0.005 to 4 μm are localized in the polyester resin matrix, and the average dispersed particle size is 0.01 to 5 μm. The present invention relates to a toner characterized by forming a domain of
[0021]
  Further, the present invention is a toner having at least (i) a domain-matrix resin composition in which a domain containing a wax is formed in a polyester resin matrix, and (ii) a colorant,
  The domain-matrix resin composition has a focused ion beam (FIB) In the observation by the processing observation apparatus, the primary dispersed particles containing the wax having a primary average dispersed particle size of 0.001 to 2 μm are localized in the polyester resin matrix, and the average dispersed particle size is 0.01 to 10 μm. The present invention relates to a toner characterized by forming a domain of
[0022]
  Further, the present invention fixes the toner image to the recording material by bringing a fixing member into contact with the surface of the toner image formed on the recording material and applying heat and pressure to the toner image. In the heat fixing method,
  When the toner image is fixed on the recording material, the coating amount per unit area of the recording material of the silicone oil supplied from the fixing member to the fixing surface of the toner image of the recording material is 0 to 1 × 10^-7g / cm²And
  The toner is (i) a toner having at least a domain-matrix resin composition in which a wax-containing domain is formed in a polyester resin matrix, and (ii) a colorant.
  Focused ion beam (F) of the tonerIB) In the observation by the processing observation apparatus, the primary dispersed particles having a wax-containing primary average dispersed particle size of 0.005 to 4 μm are localized in the polyester resin matrix, and the average dispersed particle size is 0.01 to 5 μm. It is related with the heat fixing method characterized by forming the domain of this.
[0023]
  Further, the present invention fixes the toner image to the recording material by bringing a fixing member into contact with the surface of the toner image formed on the recording material and applying heat and pressure to the toner image. In the heat fixing method,
  When the toner image is fixed on the recording material, the coating amount per unit area of the recording material of the silicone oil supplied from the fixing member to the fixing surface of the toner image of the recording material is 0 to 1 × 10^-7g / cm²And
  The toner is (i) a toner having at least a domain-matrix resin composition in which a wax-containing domain is formed in a polyester resin matrix, and (ii) a colorant.
  The domain-matrix resin composition has a focused ion beam (FIB) In the observation by the processing observation apparatus, the primary dispersed particles containing the wax having a primary average dispersed particle size of 0.001 to 2 μm are localized in the polyester resin matrix, and the average dispersed particle size is 0.01 to 10 μm. It is related with the heat fixing method characterized by forming the domain of this.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
  The present inventors are (i) a toner having at least a domain-matrix resin composition in which a wax-containing domain is formed in a polyester resin matrix, and (ii) a colorant.
  1) Focused ion beam (F) of the tonerIB) In the observation by the processing observation apparatus, the primary dispersed particles having a wax-containing primary average dispersed particle size of 0.005 to 4 μm are localized in the polyester resin matrix, and the average dispersed particle size is 0.01 to 5 μm. Forms the domain of; or
  2) The domain-matrix resin composition contains a focused ion beam (FIB) In the observation by the processing observation apparatus, the primary dispersed particles containing the wax having a primary average dispersed particle size of 0.001 to 2 μm are localized in the polyester resin matrix, and the average dispersed particle size is 0.01 to 10 μm. Forms the domain of
In the case of a toner characterized by the above, in a heat and pressure fixing means that does not use oil or uses less oil, it satisfies high gloss, excellent secondary color mixing, and color reproduction. The inventors have reached the present invention because they have obtained knowledge that can provide a toner having a wide range and excellent OHP permeability and an image forming method. Hereinafter, the present invention will be described in detail.
[0025]
Usually, the wax is used for the purpose of improving releasability from the fixing roller and improving high temperature offset resistance. Recently, in order to improve the low-temperature fixability, it has been studied to increase the compatibility with the binder and to use the plastic effect. Furthermore, for the purpose of improving fixing and offset resistance, a system using two kinds of waxes has been proposed. However, when a polyester resin is used as a main binder, these methods do not work. Styrene-acrylic resin and wax are inherently incompatible, but the difference in solubility parameter (Sp value) is not as great as that of polyester resin and wax. This seems to be because the dispersion state of the wax in the toner can be controlled by changing the composition and molecular weight of the resin and the kneading conditions at the time of forming the toner.
[0026]
The present inventors inferred as follows, and reached the present invention.
[0027]
In order to improve the fixing property, it is important to weaken the entanglement between the molecular chains by uniformly finely dispersing the wax in the toner. In order to improve the offset resistance, it is important that there is a wax in the vicinity of the toner surface that has a certain size, can be melted instantaneously when passing through the fixing roller, and can exert a releasing effect. . Further, if the wax having a certain size is not uniformly contained in each toner particle, the difference in chargeability of the toner particle becomes large, so that the so-called toner charge amount distribution becomes broad and developability is increased. Will be bad.
[0028]
Also, when using a polyester resin as the main binder, it is very difficult to control the dispersion state of the wax, unlike the case of the styrene-acrylic resin.
[0029]
Therefore, the present inventors have made an invention in which wax is finely dispersed in a styrene copolymer resin in advance and further dispersed in a toner as a aggregate having a certain size in a polyester resin as a main binder. It came.
[0030]
The styrene copolymer resin in the present invention is a styrene monomer, and one or more monomers selected from a styrene monomer, an N-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an acrylate monomer, and a methacrylate ester monomer. And are synthesized. In particular, a copolymer synthesized using at least a styrene monomer and an N-containing vinyl monomer is preferably used.
[0031]
Preferred forms include styrene monomers, (1) one or more monomers selected from acrylate monomers and methacrylate monomers, and (2) N-containing vinyl monomers, carboxyl group-containing monomers, and hydroxyl groups. It is preferable to synthesize using one or two or more monomers selected from the containing monomers.
[0032]
As a more preferable form, it is synthesized using a styrene monomer, (1) one or more monomers selected from acrylic ester monomers and methacrylic ester monomers, and (2) an N-containing vinyl monomer. More preferably.
[0033]
Further, as a more preferable form, a styrene monomer, (1) one or more monomers selected from acrylic ester monomers and methacrylic ester monomers, and (2) an N-containing vinyl monomer are used. It is preferable that the synthesized copolymer contains polyolefin (polyethylene and / or polypropylene), and it is desirable that a part of the polyolefin constitutes a grafted product by the copolymer.
[0034]
Examples of the styrene monomer constituting the copolymer resin in the present invention include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, 3 , 4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn -Styrene and its derivatives, such as nonyl styrene, pn-decyl styrene, pn-dodecyl styrene.
[0035]
Examples of N-containing vinyl monomers include amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide. Can be mentioned.
[0036]
Examples of the carboxyl group-containing monomer include unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic acid Unsaturated dibasic acid anhydrides such as acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itacon Half-esters of unsaturated dibasic acids such as acid methyl half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; dimethyl maleic acid, unsaturated dibasic such as dimethyl fumaric acid Esters; α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, the α, β-unsaturated acid Examples include anhydrides of saturated acids and lower fatty acids; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides thereof and monoesters thereof.
[0037]
Examples of the hydroxyl group-containing monomer include acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1 -Hydroxy-1-methylhexyl) styrene.
[0038]
Examples of the acrylate monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, and stearyl acrylate. And acrylic acid esters such as 2-chloroethyl acrylate and phenyl acrylate.
[0039]
Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. And methacrylic acid esters such as phenyl methacrylate.
[0040]
A preferred combination of monomers used in the copolymer resin is styrene (St) -butyl acrylate (BA) -acrylonitrile (AN). Furthermore, what was partially grafted to polyolefin using the monomer which comprises this copolymer resin is more preferable.
[0041]
Specifically, for example, a graft product is prepared on low density polyethylene using each monomer of styrene (St), butyl acrylate (BA), and acrylonitrile (AN) and a peroxide. This is dispersed in a polyester resin as a main binder. Paraffin wax is added thereto, and the paraffin wax is finely dispersed in the grafted product.
[0042]
As another method, for example, a graft product is prepared on low density polyethylene using each monomer of styrene (St), butyl acrylate (BA), and acrylonitrile (AN) and a peroxide. There, a paraffin wax is added to make a resin in which the paraffin wax is finely dispersed in St-BA-AN, and the resin is dispersed in a polyester resin as a main binder. A method of dispersing with a kneader may be used, but a method of mixing in a molten state at the time of synthesizing the polyester resin is preferable for controlling the dispersion diameter and aggregate dispersion diameter of the wax.
[0043]
Here, the reason why the St-BA-AN terpolymer resin was used is that the Sp value of this resin is located between the polyester resin and the wax. Furthermore, in order to adjust the Sp value of the St-BA binary copolymer resin, AN is used for the purpose of bringing the Sp value of the dispersing resin closer to the polyester resin with a slightly higher Sp value. Is preferable.
[0044]
In addition to the above, for the purpose of increasing the Sp value of the copolymer resin, the aforementioned N-containing vinyl monomer, carboxyl group-containing monomer, and hydroxyl group-containing monomer are used.
[0045]
In our study, the Sp value [(8 cal / cm^Three)^1/2Degree] and an Sp value close to polyester resin [(12 cal / cm^Three)^1/2It was found that the most preferable form is to use a copolymer resin of a monomer having a degree] and a styrene monomer.
[0046]
In the present invention, in surface observation using a focused ion beam (FIB) processing observation apparatus for toner, primary dispersion particles having a primary average dispersion diameter of 0.005 to 4 μm including a wax are localized and formed in a polyester resin matrix. It is necessary that the dispersed average diameter of the formed domain is 0.01 to 5 μm.
[0047]
In the polyester resin matrix, when the primary average dispersion diameter containing the wax is less than 0.005 μm and the dispersion average diameter of the domain formed by localizing the primary dispersion particles is less than 0.01 μm, the anti-offset property The improvement of sex is not enough. On the contrary, when the primary average dispersion diameter containing wax is larger than 4 μm, and when the dispersion average diameter of the domain formed by localization of the primary dispersion particles is larger than 5 μm, the effect of improving the offset resistance is seen. However, since the dispersion is poor, the charge amount distribution of the toner is broad and the developability is poor.
[0048]
Preferably, the primary average dispersion diameter including wax in the polyester resin matrix of the toner is preferably 0.01 to 3 μm, and the dispersion average diameter of the domain formed by localizing the primary dispersion particles is 0. A thickness of 0.05 to 4 μm is preferable from the viewpoint of fixability and developability.
[0049]
Furthermore, in the present invention, in order to achieve the above object, in the surface observation by the focused ion beam processing observation apparatus of the domain matrix resin composition, the primary average dispersion diameter containing the wax in the polyester resin matrix is 0.001 to 0.001. 2 μm, preferably 0.005 to 1.5 μm, and the dispersion average diameter of the domain formed by localization of the primary dispersed particles is 0.01 to 10 μm, preferably 0.05 to 8 μm. Is.
[0050]
For example, as shown in FIG. 1, the wax dispersed in St-BA-AN at the time of synthesizing the polyester resin is dispersed with primary particles of about 0.05 μm, the dispersed particles are localized, and the domain of 1-2 μm It can be seen that is formed. Furthermore, it can be seen that even in the case of kneading and heat melting to form a toner, although the primary dispersed particles are partially united, the matrix-domain structure is maintained.
[0051]
Thus, by localizing the primary dispersion particles of the wax, the wax is uniformly mixed regardless of the toner particle diameter, and the charge amount distribution becomes sharp. In addition, when passing through the fixing roller, a sufficient amount of the wax supplied from the domain is also supplied, so that the performance excellent in offset resistance is exhibited.
[0052]
In the present invention, the binder resin of the toner particles is a polyester resin having a carboxyl group, a linear polyester resin having a carboxyl group and having a molecular skeleton represented by the following formula (A), or this linear polyester: A non-linear polyester resin crosslinked with a trivalent or higher polyvalent carboxylic acid or a trivalent or higher polyhydric alcohol is preferred.
[0053]
[Chemical 1]

[Wherein, x and y are integers of 1 or more, and the average value of x + y is 2 to 4. R is H or C₁~ C₂₀Or an alkyl or alkenyl group. ]
[0054]
The polyester resin having a molecular skeleton represented by the formula (A) includes an aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, which will be described in detail later, or a metal compound of the carboxylic acid derivative When melt-kneaded at the same time, a metal ion crosslinked structure is easily formed, and a toner having a clear minimum value (G′min) in the dynamic elastic modulus curve of the toner can be satisfactorily produced.
[0055]
For example, in the dynamic elastic modulus curve of a toner similar to that in the later-described embodiment shown in FIG. 2, the dynamic elastic modulus (G ′₁₇₀) Is a dynamic elastic modulus (G ′) at a temperature of 140 ° C.₁₄₀Since the toner has high viscoelasticity at a temperature on the higher temperature side than), the toner is extremely excellent in high temperature offset resistance.
[0056]
On the other hand, a comparative toner similar to the later-described comparative toner showing viscoelasticity as shown in FIG. 3 does not have a clear minimum value in the temperature range of 100 to 200 ° C. As the toner increases, the storage elastic modulus of the toner decreases. Such a toner is inferior in high-temperature offset resistance and has a narrower fixable temperature range than the toner of the present invention.
[0057]
Why the molecular skeleton represented by the formula (A) specifically acts with an aromatic carboxylic acid derivative selected from aromatic oxycarboxylic acid and aromatic alkoxycarboxylic acid or a metal compound of the aromatic carboxylic acid derivative Although not fully known, the flexibility inherent in this molecular chain is likely to form a conformation that facilitates interaction (molecular configuration interaction), and the electron donating property of the phenyl group having an electron donating property at the p-position Moreover, it seems that the π-electron donating interaction of —CH═CR— is deeply involved.
[0058]
Examples of the divalent alcohol component for producing the polyester resin which is the main binder resin in the present invention include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3- Butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, 2-ethyl-1,3-hexanediol, bisphenol A hydroxide, and formula (B) Bisphenol derivatives represented
[0059]
[Chemical formula 2]

[Wherein, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10. ]
Is mentioned.
[0060]
Examples of the trihydric or higher alcohol component for forming the nonlinear polyester resin include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, Pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene is mentioned. The amount of trihydric or higher polyhydric alcohol used is preferably 0.1 to 1.9 mol% based on the total monomer.
[0061]
Examples of the divalent acid component for producing the polyester resin include fumaric acid, maleic acid, maleic anhydride, succinic acid, adipic acid, sebacic acid, malonic acid, and saturated C 8-22 carbon atoms. Alternatively, aliphatic acid component monomers substituted with unsaturated hydrocarbon groups; and aromatic acid component monomers include phthalic acid, isophthalic acid, phthalic anhydride, terephthalic acid, and ester derivatives thereof.
[0062]
Examples of the trivalent or higher polyvalent carboxylic acid component for forming the non-linear polyester resin include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4, and the like. -Naphthalene tricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof. The amount of the trivalent or higher polyvalent carboxylic acid component is preferably 0.1 to 1.9 mol% based on the total monomer.
[0063]
In the present invention, the number average molecular weight (Mn) is preferably 1300 to 9500 and the weight average molecular weight (Mw) is preferably 2601 to 190000 in the GPC measurement of the THF soluble content of the polyester resin.
[0064]
Further, the acid value of the polyelter resin is preferably 1 to 60 mgKOH / g, more preferably 5 to 50 mgKOH / g.
[0065]
Further, in the GPC measurement of the THF-soluble component when toner is formed, the number average molecular weight (Mn) is preferably 1500 to 10,000, and the weight average molecular weight (Mw) is preferably 3000 to 1500,000.
[0066]
When the number average molecular weight (Mn) of the polyester resin is less than 1300 or when the weight average molecular weight (Mw) is less than 2600, or when the number average molecular weight (Mn) of the toner is less than 1500 or when the weight average molecular weight (Mw) is less than 3000 In both cases, the surface of the fixed image has a high level of smoothness and the vividness of the image. However, high-temperature offset is likely to occur in durability, and long-term storage stability is reduced. There are also concerns about new problems such as the occurrence of carrier spent due to adhesion of toner components to the surface of the carrier and the carrier. Further, it is difficult to apply a shear during melting and kneading of the toner raw material during the production of the color toner particles, and the dispersibility of the colorant is likely to be lowered, so that the coloring power of the toner is lowered and the charge amount of the toner is likely to be changed.
[0067]
When the number average molecular weight (Mn) of the polyester resin exceeds 9500, or when the weight average molecular weight (Mw) exceeds 190000, or when the number average molecular weight (Mn) of the toner exceeds 10,000, or the weight average molecular weight (Mw) is In the case where it exceeds 1500,000, all have excellent anti-offset properties, but the fixing set temperature has to be increased, and further, the degree of pigment dispersion could be controlled, and the surface smoothness in the image area was lowered. As a result, the color reproducibility tends to deteriorate.
[0068]
When the acid value of the polyester resin is less than 1 mgKOH / g, an increase in the charge amount in durability, so-called charge-up is likely to occur, and it becomes difficult to maintain the image density for a long time. Further, when the acid value of the polyester resin is less than 1 mgKOH / g, it is difficult to control the wax-containing primary dispersion diameter and the domain diameter in the present invention, and when the toner is used, the respective diameters exceed 4 μm and 5 μm. Further, not only the developing property of the toner but also the storage stability is deteriorated. This is considered to be related not only to the relationship between the Sp values of the polyester resin, wax, and styrene copolymer as described above, but also to the interaction between polar groups. Particularly in a polyester resin having a low acid value (less than 5 mgKOH / g), the copolymer is preferably an N-containing monomer or a carboxyl group-containing monomer, more preferably a copolymer containing an N-containing monomer. Further, in a polyester resin having a high acid value (50 mgKOH / g or more), the copolymer is preferably an N-containing monomer or a hydroxyl group-containing monomer, more preferably a copolymer containing an N-containing monomer.
[0069]
When the acid value of the polyester resin exceeds 60 mgKOH / g, there is no tendency to charge up, but a tendency to decrease the charge amount particularly in a high temperature and high humidity environment, so-called white background fogging due to so-called charge down occurs, and It will cause a decline.
[0070]
Examples of the release agent (wax) used in the present invention include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; block copolymers of aliphatic hydrocarbon waxes; Examples thereof include waxes mainly composed of fatty acid esters such as carnauba wax, sazol wax and montanic acid ester wax; and those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax. Further, as release agents, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, and carnauvir alcohol Saturated alcohols such as ceryl alcohol and melyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide; Acid amides, saturated fatty acid bisamides such as hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylene bisoleic acid amide, N, N'-dioleyl adipic acid amide, N, N -Unsaturated fatty acid amides such as dioleyl sebacic acid amide; m-xylene bis stearic acid amide, aromatic bisamides such as N, N'-distearylisophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, stearic acid Fatty acid metal salt such as magnesium (generally called metal soap); Graft wax obtained by grafting vinyl monomer such as styrene or acrylic acid to aliphatic hydrocarbon wax; Fatty acid such as behenic acid monoglyceride and polyhydric alcohol And a partially esterified product of: methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and the like.
[0071]
Particularly preferred waxes are aliphatic hydrocarbon waxes such as paraffin wax.
[0072]
Next, the content of the earnest study on the wax dispersant used in the present invention will be described.
[0073]
In the endothermic curve at the time of temperature rise measured by DSC of the hydrocarbon wax, the maximum endothermic peak has a maximum value of 55 to 80 ° C., and 0.1 to 6% by mass based on the mass of the toner. That is good.
[0074]
When the amount of the wax is less than 0.1% by mass, the releasing effect is not obtained particularly when the application amount of the fixing oil is reduced or when it is not used at all. As a result, the saturation of the toner is impaired.
[0075]
Further, when a wax having a maximum endothermic peak of less than 55 ° C. is used, it becomes lower than the glass transition temperature of the resin used in the present invention, so that it dissolves on the surface of the toner when left in a high temperature environment, and therefore has anti-blocking performance. Is significantly worse. On the other hand, when the maximum endothermic peak is larger than 80 ° C., the wax cannot quickly move to the surface of the molten toner at the time of toner fixing and melting, and the releasability is deteriorated, so that high temperature offset is likely to occur.
[0076]
In the molecular weight distribution of hydrocarbon wax by GPC, the weight average molecular weight (Mw) is 400 to 800, the number average molecular weight (Mn) is 400 to 600, the weight average molecular weight (Mw) and the number average molecular weight (Mn). And the ratio (Mw / Mn) is preferably 1.0 to 2.0.
[0077]
When the number average molecular weight (Mn) of the hydrocarbon wax is less than 400 or when the weight average molecular weight (Mw) is less than 400, since it dissolves on the toner surface when left in a high temperature environment, the anti-blocking performance is greatly deteriorated. Become.
[0078]
Further, when the number average molecular weight (Mn) of the hydrocarbon wax exceeds 600, or when the weight average molecular weight (Mw) exceeds 800, or the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw When / Mn) exceeds 2.0, the wax cannot quickly move to the surface of the molten toner at the time of toner fixing and melting, and the releasability is deteriorated, so that high temperature offset is likely to occur.
[0079]
Since the compatibility between the polyester resin, which is the main binder in the present invention, and the hydrocarbon wax is originally poorer, the wax is segregated in the toner when added to the toner as it is. Since free wax and the like are also generated, problems such as white spots and poor charging occur as a result.
[0080]
In the molecular weight distribution by GPC of the copolymer resin in the present invention, the weight average molecular weight (Mw) is 5000 to 100,000, the number average molecular weight (Mn) is 1500 to 15000, and the weight average molecular weight (Mw) and number average. The ratio (Mw / Mn) to the molecular weight (Mn) is preferably 2 to 40.
[0081]
When the weight average molecular weight (Mw) of the copolymer resin is less than 5000, the number average molecular weight (Mn) is less than 1500, or the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is less than 2. The blocking resistance of the toner is significantly impaired.
[0082]
When the weight average molecular weight (Mw) of the copolymer resin exceeds 100,000, when the number average molecular weight (Mn) exceeds 15,000, or when the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) exceeds 40 When the hydrocarbon wax finely dispersed in the wax dispersant is fixed and melted, the wax cannot quickly move to the surface of the molten toner and the releasability is deteriorated, so that high temperature offset is likely to occur.
[0083]
The copolymer resin according to the present invention is preferably contained in the toner in an amount of 0.1 to 20% by mass based on the mass of the toner.
[0084]
When the content based on the mass of the toner in the copolymer resin according to the present invention exceeds 20% by mass, the low-temperature fixing (sharp melt property) of the polyester resin as the main binder is impaired, so the non-offset temperature region is narrow. The evil that it becomes becomes.
[0085]
The polyolefin used for the graft polymerization with the copolymer resin according to the present invention preferably has a maximum endothermic peak maximum value of 90 to 130 ° C. in the endothermic curve at the time of temperature rise measured by DSC.
[0086]
When the maximum value of the maximum endothermic peak of the polyolefin is less than 90 ° C. or exceeds 130 ° C., the branched structure in the graft copolymer with the styrene-acrylonitrile- (meth) acrylic acid copolymer is impaired. In addition, since the hydrocarbon wax is not finely dispersed, segregation of the hydrocarbon wax occurs when the toner is formed, and image defects such as white spots occur.
[0087]
In the present invention, the weight average molecular weight (Mw) in the molecular weight dispersion by GPC of the polyolefin contained in the wax dispersant is 500 to 30,000, the number average molecular weight (Mn) is 500 to 3000, and the weight average molecular weight (Mw ) And the number average molecular weight (Mn) (Mw / Mn) is 1.5 to 20, and the density is preferably a low density of 0.9 to 0.95.
[0088]
When the weight average molecular weight (Mn) of the polyolefin is less than 500, or the number average molecular weight (Mn) is less than 500 times, or the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) Is less than 1.5, or when the weight average molecular weight (Mw) exceeds 30000, or the number average molecular weight (Mn) exceeds 3000, or the weight average molecular weight (Mw) and the number average molecular weight (Mn) When the ratio (Mw / Mn) exceeds 20, the hydrocarbon wax finely dispersed during the wax dispersion does not effectively exude to the toner surface at the time of fixing, and the high temperature offset resistance deteriorates.
[0089]
In addition, when the density of the polyolefin exceeds 0.95 (not low density), the effectiveness in the graft copolymer with the copolymer resin is impaired in the branched structure. Segregation occurs and image defects such as white spots occur.
[0090]
The polyolefin is preferably contained in the toner in an amount of 0.01 to 2.0% by mass, preferably 0.1 to 2.0% by mass based on the mass of the toner.
[0091]
When the content based on the mass of the toner in the polyolefin is less than 0.01% by mass, the effect of addition is small, and when the content exceeds 2.0% by mass, this is also the same as the above result. Since the effective branch structure in the graft copolymer is impaired, the hydrocarbon wax is not finely dispersed, and segregation of the hydrocarbon wax occurs when the toner is formed, resulting in image defects such as white spots.
[0092]
The organometallic compound used in the present invention is an aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, a metal compound of the aromatic carboxylic acid derivative, and further a salicylic acid metal compound. The metal is preferably a divalent or higher valent metal atom. Mg as a divalent metal²⁺, Ca²⁺, Sr²⁺, Pb²⁺, Fe²⁺, Co²⁺, Ni²⁺, Zn²⁺, Cu²⁺Is mentioned. As a divalent metal, Zn²⁺, Ca²⁺, Mg²⁺, Sr²⁺Is preferred. Al for trivalent or higher metals³⁺, Cr³⁺, Fe³⁺, Ni³⁺Can be given. Among these metals, Al is preferable.³⁺, Cr³⁺And particularly preferred is Al.³⁺It is.
[0093]
In the present invention, the organometallic compound is particularly preferably an aluminum compound of di-tert-butylsalicylic acid.
[0094]
The salicylic acid metal compound is prepared, for example, by dissolving salicylic acid in an aqueous sodium hydroxide solution, dropping an aqueous solution in which a divalent or higher valent metal atom is melted into the aqueous sodium hydroxide solution, stirring with heating, and then adjusting the pH of the aqueous solution. After cooling to room temperature, the metal compound of aromatic salicylic acid can be synthesized by filtration and washing with water. However, it is not limited only to the above synthesis method.
[0095]
When the organic metal compound is used in an amount of 0.1 to 10% by mass based on the mass of the toner, the initial fluctuation of the toner charge amount is small, and it is easy to obtain the absolute charge amount necessary for development, resulting in reduction of fog and image density. It is preferable that the image quality does not deteriorate.
[0096]
If the content of the organometallic compound is less than 0.1% by mass (not added at all) based on the mass of the toner, the charge amount during durability becomes unstable, resulting in poor image density maintenance. Become. If the content of the organometallic compound exceeds 10% by mass on the basis of the mass of the toner, on the contrary, charge-up occurs during the endurance, leading to a decrease in image density.
[0097]
When the toner of the present invention is used as a magnetic toner, the magnetic toner particles include a magnetic material. In that case, the magnetic material also has a function as a colorant. Examples of magnetic materials include iron oxides such as magnetite, maghemite, and ferrite, and iron oxides including other metal oxides; metals such as Fe, Co, and Ni, or these metals and Al, Co, Cu, Pb, Examples thereof include alloys with metals such as Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, and V, and mixtures thereof.
[0098]
For example, as a magnetic material, triiron tetroxide (Fe_ThreeO_Four), Iron sesquioxide (γ-Fe₂O_Three), Zinc iron oxide (ZnFe₂O_Four), Iron yttrium oxide (Y_ThreeFe_FiveO₁₂), Iron cadmium oxide (CdFe₂O_Four), Gadolinium oxide (Gd)_ThreeFe_FiveO₁₂), Copper iron oxide (CuFe₂O_Four), Lead iron oxide (PbFe₁₂O₁₉), Nickel iron oxide (NiFe)₂O_Four), Neodymium iron oxide (NdFe₂O_Three), Iron barium oxide (BaFe)₁₂O₁₉), Magnesium iron oxide (MgFe₂O_Four), Iron manganese oxide (MnFe₂O_Four), Iron lanthanum oxide (LaFeO)_Three), Iron powder (Fe), cobalt powder (Co), nickel powder (Ni) and the like. The preferred magnetic material is triiron tetroxide, magnetic ferrite or gamma-iron sesquioxide fine powder.
[0099]
The magnetic material has an average particle diameter of 0.1 to 2 μm (preferably 0.1 to 0.5 μm), and a magnetic property of 1.6 to 12 kA / m (20 to 150) when applied with 796 kA / m (10 k Oersted). Oersted), saturation magnetization 50-200Am²/ Kg (preferably 50-100 Am²/ Kg), residual magnetization 2-20 Am²/ Kg is preferred.
[0100]
When the magnetic material is used as a magnetic one-component developer supported with a magnetic restraining force on a developer carrier that contains a magnet, the magnetic material should be contained in an amount of 5 to 120% by mass based on the mass of the toner. preferable.
[0101]
Further, when used as a non-magnetic one-component developer that is carried on a developer carrying member that does not have a magnet without magnetic binding force, the magnetic material is used in an amount of 0.1 to 5 based on the mass of the toner. It is preferable to contain by mass%.
[0102]
By containing within this range, it is possible to suppress the toner scattering phenomenon (stain in the machine) during durability.
[0103]
If the content of the magnetic material exceeds 5% by mass on the basis of the mass of the toner, the surface of the regulating blade or the roller carrying the toner will be remarkably damaged (scraped), causing a charging failure.
[0104]
Further, when mixed with magnetic carrier particles and used as a two-component developer, it is preferable that the magnetic material is contained in an amount of 0.1 to 5% by mass based on the mass of the toner.
[0105]
By containing within this range, the magnetic binding force with the roller carrying the developer is increased, so that the toner scattering phenomenon (in-machine contamination) at the time of durability can be suppressed.
[0106]
When the content of the magnetic material exceeds 5% by mass on the basis of the mass of the toner, the magnetic binding force with the roller carrying the developer increases excessively, leading to a decrease in image density.
[0107]
As the colorant used in the present invention, pigments and / or dyes can be used.
[0108]
For example, as the dye, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modern Tread 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modern Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Basic green 6 etc. are mentioned.
[0109]
As pigments, mineral fast yellow, navel yellow, naphthol yellow S, hansa yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G, permanent red 4R, watch red red calcium salt , Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, Pigment Green B, Malachite green lake, final yellow green G, etc. are mentioned.
[0110]
Further, when used as a full-color image forming toner, examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 163, 184, 202, 206, 207, 209, 221, 238, 254, 269, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
[0111]
Such a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together. Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1; I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28 can be mentioned.
[0112]
Examples of the color pigment for cyan include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Acid Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.
[0113]
Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 83, 93, 97, 180, C.I. I. Vat yellow 1, 3, 20 etc. are mentioned.
[0114]
The amount of the colorant used is 1 to 15 parts by mass, preferably 3 to 12 parts by mass, and more preferably 4 to 10 parts by mass with respect to 100 parts by mass of the binder resin.
[0115]
When the content of the colorant is more than 15 parts by mass, the transparency is lowered, and in addition, the reproducibility of intermediate colors as typified by human skin color is likely to be lowered, and further, the charging property of the toner is stabilized. And the target charge amount is difficult to obtain.
[0116]
When the content of the colorant is less than 1 part by mass, it is difficult to obtain the desired coloring power, and it is difficult to obtain a high-quality image with a high image density.
[0117]
In order to improve image quality, it is preferable that a fluidity improver is externally added to the toner particles.
[0118]
As the fluidity improver, the fluidity can be increased by adding the toner particles externally before and after the addition. For example, fluororesin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder; silica fine powder by wet production method, silica fine powder such as silica fine powder by dry production method, these silica fine powders as silane coupling agent, Examples thereof include a treated silica fine powder subjected to a surface treatment with a treating agent such as a titanium coupling agent and silicone oil; a titanium oxide fine powder; an alumina fine powder, a treated titanium oxide fine powder, and a treated alumina oxide fine powder.
[0119]
The fluidity improver has a specific surface area of 30 m due to nitrogen adsorption measured by the BET method.²/ G or more, preferably 50 m²/ G or more gives good results. The fluidity improver is used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the toner particles.
[0120]
Toner particles are sufficiently mixed with a binder resin, colorant, organometallic compound, and other optional ingredients using a mixer such as a Henschel mixer or ball mill, and then melted using a heat kneader such as a kneader or extruder. Toner particles having a predetermined average particle diameter can be produced by summing and kneading, cooling and solidifying the melt-kneaded product, pulverizing the solidified product, and classifying the pulverized product.
[0121]
Further, the fluidity improver and the toner particles can be sufficiently mixed by a mixer such as a Henschel mixer to obtain a toner having the fluidity improver on the toner particle surface.
[0122]
In the present invention, the weight average particle diameter (D_Four) Is 3.0 to 15.0 μm, preferably 4.0 to 12.0 μm.
[0123]
Weight average particle diameter of toner (D_Four) Is less than 3.0 μm, it becomes difficult to achieve stabilization of charge, and fog and toner scattering tend to occur in durability.
[0124]
Weight average particle diameter of toner (D_Four) Exceeds 15.0 μm, the reproducibility of the halftone portion is greatly reduced, and the obtained image becomes a rough image.
[0125]
Next, a method for forming a full color image by electrophotography using the toner of the present invention will be described with reference to FIG.
[0126]
FIG. 4 is a schematic configuration diagram illustrating an example of an image forming apparatus for forming a full-color image by electrophotography. The image forming apparatus shown in FIG. 4 is used as a full-color copying machine or a full-color printer. In the case of a full-color copying machine, as shown in FIG. 3, a digital color image reader unit is provided at the top and a digital color image printer unit is provided at the bottom.
[0127]
In the image reader unit, the original 30 is placed on the original platen glass 31 and exposed and scanned by the exposure lamp 32, whereby the reflected light image from the original 30 is condensed on the full color sensor 34 by the lens 33, and the color color separation image signal is obtained. Get. The color separation image signal is processed by a video processing unit (not shown) through an amplifier circuit (not shown) and sent to a digital image printer unit.
[0128]
In the image printer unit, the photosensitive drum 1 as an image carrier has a photosensitive layer having, for example, an organic photoconductor, and is carried rotatably in the direction of the arrow. Around the photosensitive drum 1, there are a pre-exposure lamp 11, a corona charger 2, a laser exposure optical system 3, a potential sensor 12, four developing devices 4Y, 4C, 4M, and 4B of different colors, and an on-drum light amount detecting means 13. A transfer device 5 and a cleaning device 6 are arranged.
[0129]
In the laser exposure optical system, an image signal from the reader unit is converted into an image scan exposure optical signal by a laser output unit (not shown), and the converted laser beam is reflected by the polygon mirror 3a, and the lens 3b and The image is projected onto the surface of the photosensitive drum 1 via the mirror 3c.
[0130]
At the time of image formation, the printer unit rotates the photosensitive drum 1 in the direction of the arrow, neutralizes the charge with the pre-exposure lamp 11, and then uniformly charges the photosensitive drum 1 with the charger 2, so that the optical image E for each separated color. To form an electrostatic charge image on the photosensitive drum 1.
[0131]
Next, a predetermined developing device is operated to develop the electrostatic image on the photosensitive drum 1 to form a toner image with toner on the photosensitive drum 1. The developing units 4Y, 4C, 4M, and 4B perform development by approaching the photosensitive drum 1 alternatively according to the respective separation colors by the operations of the eccentric cams 24Y, 24C, 24M, and 24B.
[0132]
The transfer device includes a transfer drum 5a, a transfer charger 5b, an adsorption charger 5c for electrostatically adsorbing a transfer material as a recording material, and an adsorption roller 5g opposed thereto, an inner charger 5d, an outer charger 5e, A separation charger 5h is provided. The transfer drum 5a is pivotally supported so as to be rotationally driven, and a transfer sheet 5f, which is a transfer material carrier that carries a transfer material in an opening area of a peripheral surface thereof, is integrally adjusted on a cylinder. A resin film such as a polycarbonate film is used for the transfer sheet 5f.
[0133]
The transfer material is conveyed from the cassette 7a, 7b or 7c to the transfer drum 5a through the transfer sheet conveyance system, and is carried on the transfer drum 5a. The transfer material carried on the transfer drum 5a is repeatedly conveyed to the transfer position facing the photosensitive drum 1 as the transfer drum 5a rotates, and is transferred onto the transfer material by the action of the transfer charger 5b in the process of passing through the transfer position. The toner image on the photosensitive drum 1 is transferred onto the photosensitive drum 1.
[0134]
The toner image may be directly transferred from the photosensitive member to the transfer material, or the toner image on the photosensitive member may be transferred to the intermediate transfer member, and the toner image may be transferred from the intermediate transfer member to the transfer material.
[0135]
The above image forming process is repeated for yellow (Y), magenta (M), cyan (C) and black (B) to obtain a color image in which four color toner images are superimposed on the transfer material on the transfer drum 5. It is done.
[0136]
The transfer material onto which the four color toner images have been transferred in this way is separated from the transfer drum 5a by the action of the separation claw 8a, the separation push-up roller 8b, and the separation charger 5h, and is sent to the heating and pressure fixing device 9. Then, the toner is mixed with color, developed, and fixed to a transfer material by heat and pressure fixing to form a full-color fixed image, which is then discharged onto the tray 10 to complete the formation of the full-color image.
[0137]
At this time, the fixing operation speed in the heat and pressure fixing device 9 is performed at a slower speed (for example, 90 mm / sec) than the process speed (for example, 160 mm / sec) of the main body. This is because when an unfixed image in which two to four layers of toner are laminated is melted and mixed, a sufficient amount of heating must be given to the toner, so that the toner is heated by fixing at a speed slower than the developing speed. The amount is increased.
[0138]
In FIG. 5, a fixing roller 39 as a fixing unit includes, for example, a 2 mm thick RTV (room temperature vulcanization type, JIS-A hardness 20) silicone rubber layer 42 on an aluminum cored bar 41 having a thickness of 5 mm. And a polytetrafluoroethylene (PTFE) layer 43 having a thickness of 50 μm.
[0139]
On the other hand, the pressure roller 40 as a pressure means is, for example, an RTV silicone rubber layer 45 (rubber hardness JIS-A hardness 40) having a thickness of 2 mm on an aluminum core metal 44 having a thickness of 5 mm, and a thickness on the outside thereof. It has a 150 μm PTFE layer.
[0140]
In FIG. 5, the outer diameter of both the fixing roller and the pressure roller is 60 mmφ. However, since the pressure roller has higher hardness, in the paper discharge test with a blank paper, the line connecting the center lines of both rollers is used. From the vertical line, the paper discharge direction is the pressure roller side. Setting the paper discharge direction to the pressure roller side is extremely important for preventing the fixing support from being wrapped around the fixing support when a copy image having a large image area is fixed. As a means for setting the paper discharge direction to the pressure roller side, the above-mentioned method of making the hardness difference, the method of making the diameter of the pressure roller smaller than the fixing roller, or the setting temperature on the pressure roller side than the fixing roller is used. For example, there is a method in which a very small amount of paper is used by evaporating more water on the back surface of the fixing paper, that is, on the pressure roller side.
[0141]
The fixing roller 39 is provided with a halogen heater 46 as a heat generating means, and the pressure roller 40 is similarly provided with a halogen heater 47 in a cored bar for heating from both sides. The thermistors 48a and 48b in contact with the fixing roller 39 and the pressure roller 40 detect the temperatures of the fixing roller 39 and the pressure roller, and the halogen heaters 46 and 47 are controlled by the control devices 49a and 49b based on the detected temperatures. Then, both the temperature of the fixing roller 39 and the temperature of the pressure roller 40 are controlled so as to be maintained at a constant temperature (for example, 160 ° C. ± 10 ° C. The fixing roller 39 and the pressure roller 40 are not shown. )) At a total pressure of about 390 N (40 kgf).
[0142]
In FIG. 5, C is a fixing roller cleaning device using an oil-impregnated paper web, and C1 is a cleaning blade for removing oil and dirt adhering to the pressure roller. The oil for impregnating the paper web uses 50 to 3000 cs silicone oil (silicone oils such as dimethyl silicone oil and diphenyl silicone oil). The quality of the fixed image (particularly uniform gloss, oil marks) becomes high. When oil is not applied, it is preferable to remove the C cleaning device, use a paper or cloth web not impregnated with oil, or use a cleaning blade, a cleaning pad, or a cleaning roller.
[0143]
The cleaning device C cleans the nonwoven web 56 made of Nomex (trade name) by pressing it against the fixing roller 39 with the pressing roller 55. The web 56 is appropriately wound by a winding device (not shown) so that toner or the like does not accumulate at the contact portion with the fixing roller 39.
[0144]
Since the toner of the present invention is excellent in low-temperature fixability and high-temperature offset resistance, the amount of release agent applied can be reduced, and the amount of dirt on the cleaning device is also small.
[0145]
The toner image of the toner of the present invention is preferably heat-pressed and fixed under a temperature condition of a surface temperature of the fixing roller of 150 ° C. ± 30 ° C., and when the toner image is fixed onto the recording material, The coating amount of the silicone oil supplied to the fixing surface of the toner image of the material per unit area of the recording material is 0 to 1 × 10^-7g / cm²It is good to be.
[0146]
Application amount is 1 × 10^-7g / cm²When the value exceeds 1, the glare of the recording material is large, and particularly the visibility of the character image is significantly impaired.
[0147]
By the image forming process described above, the color toner image having the toner of the present invention is fixed on the recording material sheet, whereby a color image formed on the recording sheet is obtained.
[0148]
A method for measuring physical properties of the binder resin and toner particles will be described below.
[0149]
(1)Cross section observation method of toner and resin by focused ion beam processing observation apparatus
Processing and observation are performed using a focused ion beam processing observation apparatus (FIB apparatus) and FB-2000A (manufactured by Hitachi, Ltd.). Next, an example of a method for producing a measurement material is shown.
[0150]
The sample was prepared by applying a carbon paste or applying a conductive tape on the FIB sample stage, fixing a small amount of the measurement sample thereon, and depositing it.
[0151]
After protecting the processed surface of the manufactured sample with an FIB apparatus, the cross section of the sample is cut out as rough processing, and then processed with intermediate processing, finishing processing, and beam energy reduced. In the final observation, observation is performed using a beam having the lowest energy.
[0152]
The primary average dispersion particle diameter and domain diameter (localized average dispersion diameter) containing the wax in the present invention are determined as follows.
[0153]
A sample obtained by pulverizing the domain-matrix resin composition of the present invention to a size of about 10 μm is used as a sample. The observation procedure is performed as described above. After the end of the first observation, for example, a primary dispersed particle size including a certain focused domain and a wax is measured. Next, while adjusting the energy of the beam, it is cut out little by little, and the domain of interest and the change in the primary dispersion particle size are measured, and the observation screen vertical and horizontal (xy) direction and depth (depth) (z ) Get the direction diameter. The maximum diameter of the domain and the primary dispersion diameter is obtained by plotting these measurement results as shown in FIG. 6 and by interpolation or extrapolation. The number of measurements is 50 for each sample, 10 for each domain and primary dispersed particle, and 5 for each sample. The average of these maximum diameters was calculated and used as the primary average dispersion diameter and the average domain diameter, respectively.
[0154]
The same method is used for toner. However, in the toner, a case where the primary dispersed particles are partially united is observed, but it is regarded as one primary dispersed particle and an average diameter is obtained.
[0155]
(2)Measurement of acid value (JIS acid value)
2-10 g of sample is weighed into a 200-300 ml Erlenmeyer flask, and about 50 ml of a mixed solvent of methanol: toluene = 30: 70 is added to dissolve the resin. If solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% bromthymol blue and phenol red, titration is performed with a pre-standardized N / 10 caustic potash to alcohol solution, and the acid value is obtained from the consumption of the alcohol potash solution by the following calculation.
[0156]
Acid value = KOH (ml) × f × 56.1 / sample weight
(Where f is a factor of N / 10KOH)
[0157]
(3)Sample preparation for molecular weight distribution measurement
When measuring the molecular weight of the toner, it is dissolved in THF, extracted by Soxhlet reflux for 6 hours, and the dissolved product is measured as a sample.
[0158]
In the sample for measuring polyester, copolymer resin, and wax, first, the toner is separated into ethyl acetate soluble and insoluble components, and the soluble component is used as a polyester resin molecular weight measurement sample. The insoluble matter is further separated after removal of the solvent into a THF soluble component and an insoluble component, and the molecular weight is measured using the soluble component as a copolymer resin and the insoluble component as a wax.
[0159]
(4)Measurement of molecular weight by GPC (polyester resin, copolymers)
The molecular weight of the chromatogram obtained by gel permeation chromatography (GPC) is measured under the following conditions.
[0160]
Resin prepared by stabilizing the column in a heat chamber at 40 ° C., and flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min to the column at this temperature to adjust the sample concentration to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 to 200 μl of a THF sample solution. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Industry Co., Ltd.²2.1 × 10^Three, 4 × 10^Three, 1.75 × 10^Four, 5.1 × 10^Four1.1 × 10^Five, 3.9 × 10^Five8.6 × 10^Five, 2 × 10⁶, 4.48 × 10⁶It is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
[0161]
As column, 10^Three~ 2x10⁶In order to accurately measure the molecular weight region, it is preferable to combine a plurality of commercially available polystyrene gel columns, for example, μ-styrgel 500, 10 manufactured by Waters.^Three, 10^Four, 10^FiveAnd combinations of shodex KA-801, 802, 803, 804, 805, 806 and 807 manufactured by Showa Denko KK are preferred.
[0162]
(5)Measurement of molecular weight by GPC (polyolefin, hydrocarbon waxes)
(GPC measurement conditions)
・ Apparatus: GPC-150 (Waters)
Column: GMH-HT 30 cm 2 series (manufactured by Tosoh Corporation)
・ Temperature: 135 ℃
・ Solvent: o-dichlorobenzene (0.1% Aiosol added)
・ Flow rate: 1.0 ml / min
・ Sample: 0.4 ml of 0.15% sample was injected
Measurement is performed under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used in calculating the molecular weight of the sample. Furthermore, it is calculated by polystyrene conversion using a conversion formula derived from the Mark-Houwink viscosity formula.
[0163]
  (6)Measurement of maximum endothermic peaks of wax and toner
  DifferentialScanning calorieIt measures using a measuring apparatus (DSC measuring apparatus) and DSC-7 (made by Perkin Elmer). The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min at room temperature and normal humidity within a measurement temperature range of 30 to 200 ° C. In this temperature raising process, an endothermic peak of a main peak in the temperature range of 30 to 160 ° C. is obtained. Needless to say, the endothermic peak is a temperature showing a maximum value in the endothermic peak. The endothermic peak of polyolefin is often low in content and difficult to detect. In such a case, the polyester resin is dissolved and separated with ethyl acetate, and measurement is preferably performed using a so-called concentrated sample (hydrocarbon wax may have an endothermic peak measured in the same way. If you have difficulty).
[0164]
(7)Measurement of toner particle or toner particle size distribution
As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Inc.) is used. About 1% NcCl aqueous solution is prepared using 1st grade sodium chloride as electrolyte solution. For example, ISOTON (registered trademark) -II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzenesulfone hydrochloride) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the volume and the number of toner particles are measured for each channel by using the measuring apparatus with a 100 μm aperture as the aperture. Thus, the toner volume distribution and number distribution are calculated. Then, the mass-based toner particles obtained from the volume distribution of the toner particles or the mass average particle diameter (D_Four) And volume average particle size (D_v) (The median value of each channel is the representative value for each channel).
[0165]
As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32-40.30 μm are used.
[0166]
(8)Measurement of triboelectric charge
FIG. 7 is an explanatory diagram of an apparatus for measuring the triboelectric charge amount. In a metal measuring container 82 having a 500-mesh screen 83 on the bottom, a mixture of a sample and a carrier whose triboelectric charge is to be measured, that is, in the case of toner, a toner to carrier mass ratio of 1:19. In the case of a mixture or external additive, a 1:99 mixture is placed in a polyethylene bottle in a 50 to 100 ml container and shaken by hand for about 10 to 40 seconds. Put 5 to 1.5 g and make a metal lid 84. Weigh the entire measurement container 82 at this time W₁(G). Next, in the suction machine 81 (at least the part in contact with the measurement container 82 is suctioned), the pressure of the vacuum gauge 85 is set to 250 mmAq by suctioning from the suction port 57 and adjusting the air volume control valve 86. In this state, the toner is removed by suction for 2 minutes. The potential of the electrometer 89 at this time is set to V (volt). Here, 88 is a capacitor, and the capacity is C (mF). Also, weigh the entire measurement container after suction.₂(G). The triboelectric charge amount (mC / kg) of this sample is calculated as follows.
[0167]
Sample triboelectric charge (mC / kg) = C × V / (W₁-W₂)
(However, the measurement conditions are 23 ° C. and 60% RH.)
[0168]
【Example】
Examples of the toner and heat fixing method of the present invention will be described below, but the present invention is not limited to these examples.
[0169]
[Examples of resin production]
・ Low-density polyethylene 20 parts by mass
(Mw 1400, Mn 850, endothermic peak 100 ° C.)
・ Styrene 64 parts by mass
・ 13.5 parts by mass of n-butyl acrylate
・ Acrylonitrile 2.5 parts by mass
In an autoclave and N inside the system₂After replacement, the temperature was maintained at 180 ° C. with stirring. Into the system, 50 parts by mass of a 2% by mass t-butyl hydroperoxide xylene solution was continuously added dropwise for 5 hours. After cooling, the solvent was separated and removed, and the copolymer was partially grafted with polyethylene. A mixed resin with a polymer resin and unreacted polyethylene was obtained. The molecular weight of the copolymer in the mixed resin was measured and found to be Mw 7000 and Mn 3000.
[0170]
next,
・ Terephthalic acid 28mol%
N-dodecenyl succinic acid 17 mol%
・ Trimellitic anhydride 5 mol%
・ Bisphenol represented by formula (B) 50 mol%
(R: propylene, x + y≈2.2)
Was subjected to condensation polymerization to obtain a polyester resin having Mw of 17,000, Mn of 7000, a glass transition temperature (Tg) of 65 ° C. and an acid value of 12 mgKOH / g. While the polyester resin was melted at 150 ° C. in the reaction system, 5 parts by mass of the mixed resin was added to and mixed with 100 parts by mass of the polyester resin. Furthermore, 4 parts by mass of hydrocarbon wax (Mw 600, Mn 510, endothermic peak 64 ° C.) was added to and mixed with 100 parts by mass of the polyester resin.
[0171]
The resin obtained as described above is referred to as Resin I.
[0172]
When this resin I was observed by FIB processing, the primary average dispersion diameter including wax in the polyester resin matrix was 0.04 μm, and the domain diameter was 2.5 μm.
[0173]
In the same manner, various conditions such as monomer composition, initiator type / amount, polyolefin type / amount, mixing ratio, polyester resin composition, hydrocarbon wax type / amount, reaction temperature, etc. were changed, and Table 1 Domain-matrix resin compositions II to IX shown were obtained.
[0174]
[Table 1]

[0175]
<Example 1>
A toner was prepared according to the formulation shown in Table 2. Here, black, cyan, yellow and magenta pigments are pre-masterbatched at a high concentration of 30% by mass using the same polyester resin as the main binder in order to improve dispersibility and increase saturation and brightness. The resin of the present invention and the master batch were weighed so that the amount of pigment shown in Table 2 was obtained, a charge control agent was added, and the mixture was mixed with a Henschel mixer. Thereafter, the mixture was melt-kneaded by a biaxial extrusion kneader, cooled, pulverized, and classified to obtain black, cyan, yellow, and magenta toner classified products shown in Table 2.
[0176]
To these toner classified products, 1.0% by mass of titanium oxide surface-treated with 10% by mass of isobutyltrimethoxysilane was externally added and mixed to obtain toners of respective colors.
[0177]
Further, these externally added toner and ferrite carrier particles (average particle size 50 μm) surface-coated with a silicone resin were mixed so that the toner concentration was 6% by mass to obtain a two-component developer for full color.
[0178]
[Table 2]

[0179]
Evaluation of the fixable temperature range is performed by using a commercially available plain paper full-color copier (color laser copier CLC900; manufactured by Canon) with the fixing unit removed, and using the above two-component cyan developer, the unfixed image is at room temperature and normal humidity (N / N; 23 ° C., 60%), and the image was evaluated by measuring the gloss (glossiness) by outputting a fixed image while changing the set temperature with a fixing tester having the configuration shown in FIG. An area having a gloss of 7% or more was defined as a mixed color area.
[0180]
Further, the fixing unit (with the web oil application device removed and the cleaning pad attached) was mounted, and normal temperature and low humidity (N / L; 23 ° C., 5%) and high temperature and high humidity (H / H; 30 ° C., 80 %) Image endurance test in the environment.
[0181]
Regarding the gloss (glossiness) measurement, a VG-10 gloss meter (manufactured by Nippon Denshoku Co., Ltd.) is used, and each solid image used for chromaticity measurement is measured as a sample.
[0182]
As a measurement, first, it is set to 6V by a constant voltage device. Next, the light projection angle and the light reception angle are adjusted to 60 °. Using the zero point adjustment and the standard plate, after the standard setting, the sample image is placed on the sample table, and the measurement is performed by superposing three sheets of white paper on top of each other, and the numerical value shown on the marking unit is read in units of%. At this time, the S and S / 10 switch SW is set to S, and the angle and sensitivity switch SW is set to 45-60.
[0183]
These evaluation results are shown in Table 4. The image density was measured with a color reflection densitometer (X-RITE 404A; manufactured by X-Rite).
[0184]
As shown in Table 4, the fixing characteristics and the mixed color area were sufficient, the OHT light transmittance was high, and the color reproduction range of the transmitted image of the OHT mixed color image was sufficiently wide. Also in the image durability evaluation at N / L and H / H, stable developability was exhibited, and good storage stability was obtained. Further, even in a full color image at N / L and H / H, the color reproduction region is wide. Furthermore, the cleaning pad attached to the fixing device was less contaminated and was at a level with no problem.
[0185]
<Examples 2 to 7>
Cyan toners 2 to 7 were prepared in the same manner as in Example 1 with the formulation shown in Table 3. These toners and developers were evaluated in the same manner as in Example 1, and the results are shown in Table 4.
[0186]
<Comparative Example 1>
88 parts by mass of the polyester resin used in Example 1, 5.7 parts by mass of hydrocarbon wax, 13.3 parts by mass of cyan master batch and 3 parts by mass of the charge control agent were mixed with a Henschel mixer, and then the same as in Example 1. Toner and developer were prepared and evaluated in the same manner.
[0187]
In the observation by FIB, the primary dispersion average diameter of the wax was 4.5 μm, and the domain formed by the primary dispersion particles was not observed.
[0188]
Table 4 shows the results of fixing evaluation and image evaluation.
[0189]
[Table 3]

[0190]
[Table 4]

[0191]
【The invention's effect】
According to the present invention, it is possible to obtain a color toner having good transparency with OHP, excellent offset resistance and fixability, and having developability similar to that before leaving after standing for a long time.
[Brief description of the drawings]
FIG. 1 is a diagram showing the formation of a wax dispersion or domain drawn based on a photograph by processing observation.
FIG. 2 is a diagram illustrating an example of a dynamic elastic modulus curve of the toner of the present invention.
FIG. 3 is a diagram illustrating an example of a dynamic elastic modulus curve of a conventional toner.
FIG. 4 is a schematic cross-sectional view showing an example of an image forming apparatus using the toner of the present invention.
FIG. 5 is a schematic explanatory diagram illustrating an example of a heat and pressure fixing unit.
FIG. 6 is a diagram showing an example of plotting data in measurement of a primary average dispersion diameter and a domain diameter containing wax.
FIG. 7 is a schematic view of an apparatus for measuring the triboelectric charge amount of toner.
[Explanation of symbols]
1 Photosensitive drum (image carrier)
4 Developer
9 Heating and pressure fixing device

Claims (17)

(I) a toner having at least a domain-matrix resin composition in which a wax-containing domain is formed in a polyester resin matrix; and (ii) a colorant;
When observing the toner with a focused ion beam (FIB) processing observation device, the primary dispersion particles having a primary average dispersion particle size of wax ranging from 0.005 to 4 μm are localized in the polyester resin matrix. A toner having a domain having a particle size of 0.01 to 5 μm.   In the surface observation of the toner by a focused ion beam (FIB) processing observation apparatus, the primary dispersed particles having a wax-containing primary average dispersed particle size of 0.01 to 3 μm are localized and averaged in the polyester resin matrix. The toner according to claim 1, wherein a domain having a dispersed particle diameter of 0.05 to 4 μm is formed. (I) a toner having at least a domain-matrix resin composition in which a wax-containing domain is formed in a polyester resin matrix; and (ii) a colorant;
In the domain-matrix resin composition, when observed with a focused ion beam (FIB) processing observation apparatus, primary dispersed particles containing a wax having a primary average dispersed particle size of 0.001 to 2 μm are locally contained in the polyester resin matrix. A toner characterized by being formed to form a domain having an average dispersed particle diameter of 0.01 to 10 μm. The domain-matrix resin composition has a primary dispersion with a primary average dispersion particle size of 0.005 to 1.5 μm including a wax in the polyester resin matrix in surface observation using a focused ion beam (FIB) processing observation apparatus. The toner according to claim 3 , wherein the particles are localized to form a domain having an average dispersed particle diameter of 0.05 to 8 μm. The domain-matrix resin composition comprises a styrene monomer and one or more monomers selected from an N-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an acrylate monomer, and a methacrylate ester monomer. the toner according to any one of claims 1 to 4, characterized in that it contains at least the copolymeric synthesized using. The toner according to claim 5 , wherein the copolymer includes at least a copolymer synthesized using at least a styrene monomer and an N-containing vinyl monomer. The toner includes a styrene monomer, (1) one or more monomers selected from an acrylate monomer and a methacrylate ester monomer, and (2) an N-containing vinyl monomer, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer. the toner according to any one of claims 1 to 6, characterized in that the copolymer synthesized by using the one or more monomers selected from monomers containing at least. The toner is a copolymer synthesized using a styrene monomer, (1) one or more monomers selected from acrylic acid ester monomers and methacrylic acid ester monomers, and (2) an N-containing vinyl monomer. the toner according to any one of claims 1 to 7, characterized in that it contains at least a polymer. The toner is synthesized using a styrene monomer and one or more monomers selected from an N-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an acrylate monomer, and a methacrylate ester monomer. copolymer, and the toner according to any one of claims 1 to 4, characterized by containing a wax dispersant having a polyolefin. The toner has a styrene monomer, a copolymer synthesized by using at least the N-containing vinyl monomer, and, according to claim 9, characterized by containing a wax dispersant having a polyolefin toner. The toner includes a styrene monomer, (1) one or more monomers selected from an acrylate monomer and a methacrylate ester monomer, and (2) an N-containing vinyl monomer, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer. copolymer synthesized by using the one or more monomers selected from the monomers, and the toner according to claim 9 or 10, characterized by containing a wax dispersant having a polyolefin . The toner is a copolymer synthesized using a styrene monomer, (1) one or more monomers selected from acrylic acid ester monomers and methacrylic acid ester monomers, and (2) an N-containing vinyl monomer. polymers, and the toner according to any one of claims 9 to 11 is characterized by containing a wax dispersant having a polyolefin. In the endothermic curve at the time of Atsushi Nobori measured by DSC of the polyolefin, the toner according to any one of claims 9 to 12 maximum value of the maximum endothermic peak is characterized in that it is in the 90 to 130 ° C.. In molecular weight distribution by GPC of the polyolefin has a weight average molecular weight (Mw) of 500 to 30,000, a number average molecular weight (Mn) according to any one of claims 9 to 13, characterized in that 500 to 3000 toner. The toner according to any one of claims 9 to 14 , wherein the polyolefin is contained in an amount of 0.01 to 2.0% by mass based on the mass of the toner. The polyolefin toner according to any one of claims 9 to 14, characterized in that it is contained 0.1 to 2.0 wt% of weight of the toner as a reference. In a heat fixing method for fixing a toner image to the recording material by bringing a fixing member into contact with the surface of the toner image formed on the recording material and applying heat and pressure to the toner image.
When the toner image is fixed on the recording material, the coating amount per unit area of the recording material of the silicone oil supplied from the fixing member to the fixing surface of the toner image of the recording material is 0 to 1 × 10 ⁻⁷ g / cm. ² and
The toner is a heat fixing method comprising toner der Rukoto according to any one of claims 1 to 16.

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